Guest-compound-enveloping polymer-metal-complex crystal, method for producing same, method for preparing crystal structure analysis sample, and method for determining molecular structure of organic compound

ABSTRACT

The present invention is a method for preparing a crystal structure analysis sample in which a molecule of an organic compound for which a molecular structure is to be determined, is arranged in pores and voids of a polymer-metal complex crystal in an ordered manner. The method includes immersing a polymer-metal complex crystal including a guest compound in a solvent solution that includes the organic compound, the polymer-metal complex crystal including a guest compound being the polymer-metal complex crystal comprising a polymer-metal complex that comprises a ligand having two or more coordinating moieties. A ratio of an amount of the guest compound (A) present in the pores and the voids to a total amount of the guest compound included in the pores and the voids being 60 mol % or more.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/426,809, filed on Mar. 9, 2015 now U.S. Pat. No. 10,190,952, which isa 371 of International Application No. PCT/JP2013/056370, filed on Mar.7, 2013, which claims the benefit of priorities from the prior JapanesePatent Application No. 2012-270199, filed on Dec. 11, 2012, and JapanesePatent Application No. 2012-197911, filed on Sep. 7, 2012 the entirecontents of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a polymer-metal complex crystalincluding a guest compound that is useful as a material for preparing acrystal structure analysis sample that is used to determine themolecular structure of a trace amount of organic compound, a method forproducing the same, a method for preparing a crystal structure analysissample that utilizes the polymer-metal complex crystal including a guestcompound, and a method for determining the molecular structure of anorganic compound that utilizes a crystal structure analysis sampleobtained using the method for preparing a crystal structure analysissample.

BACKGROUND ART

In recent years, a physiologically active substance that is derived froma marine organism or the like and found in a trace amount has beenexpected to be a resource for agricultural chemicals, medicines, and thelike (Patent Documents 1 and 2). Therefore, it has become very importantto accurately and efficiently determine the molecular structure of sucha trace amount of organic compound in order to develop a novelagricultural chemical or medicine, for example.

When producing an agricultural chemical or a medicine, it is necessaryto accurately identify a trace amount of impurities included in theagricultural chemical, medicine, or raw material in order to improvesafety.

It has also been desired to identify a trace amount of impuritiesincluded in a raw material used to produce electronic parts, and reducethe amount of impurities along with a recent improvement in performanceof electronic parts.

Specifically, it has been desired to accurately and efficientlydetermine the molecular structure of a trace amount of organic compoundin various fields.

X-ray single crystal structure analysis has been known as a method fordetermining the molecular structure of an organic compound. Themolecular structure of an organic compound can be accurately determinedusing X-ray single crystal structure analysis when it is possible toprepare a high-quality single crystal.

However, when the amount of organic compound is very small, and it isimpossible to obtain a sufficient amount of single crystal, it isdifficult to employ X-ray single crystal structure analysis fordetermining the molecular structure of the organic compound. It isdifficult to prepare a single crystal when the organic compound forwhich the molecular structure is to be determined is liquid at aboutroom temperature (i.e., when the melting point of the organic compoundis equal to or lower than room temperature).

RELATED-ART DOCUMENT Patent Document

-   Patent Document 1: JP-A-2006-232738-   Patent Document 2: JP-A-2010-090141

SUMMARY OF THE INVENTION Technical Problem

The invention was conceived in view of the above situation. An object ofthe invention is to provide a polymer-metal complex crystal including aguest compound that makes it possible to prepare a crystal structureanalysis sample that is useful for determining the molecular structureof a trace amount of organic compound, a method for producing the same,a method for preparing a crystal structure analysis sample, and a methodfor determining the molecular structure of an organic compound thatutilizes a crystal structure analysis sample obtained using the methodfor preparing a crystal structure analysis sample.

Solution to Problem

The inventors of the invention conducted extensive studies in order tosolve the above technical problem. As a result, the inventors found thata sample that is suitable for crystal structure analysis that is used todetermine the molecular structure of a trace amount of organic compoundcan be efficiently prepared by utilizing a polymer-metal complex crystalincluding a guest compound that includes a polymer-metal complex havinga three-dimensional network structure, and having pores and voids thatare three-dimensionally arranged in the three-dimensional networkstructure in an ordered manner, wherein a specific guest compound isincluded in the pores and the like in an amount equal to or more than agiven amount. This finding has led to the completion of the invention.

Several aspects of the invention provide the following polymer-metalcomplex crystal including a guest compound (see [1] to [8]), method forproducing a polymer-metal complex crystal including a guest compound(see [10]), method for preparing a crystal structure analysis sample(see [11] to [20]), and a method for determining the molecular structureof an organic compound (see [21]).

[1] A polymer-metal complex crystal including a guest compound, thepolymer-metal complex crystal including a polymer-metal complex thatincludes a ligand having two or more coordinating moieties, and a metalion that serves as a center metal, the polymer-metal complex having athree-dimensional network structure that is formed by the metal ion andthe ligand that is coordinated to the metal ion, and having pores andvoids that are three-dimensionally arranged in the three-dimensionalnetwork structure in an ordered manner, at least one compound selectedfrom the group consisting of an aliphatic hydrocarbon, an alicyclichydrocarbon, an ether, an ester, an aromatic hydrocarbon, a halogenatedhydrocarbon, and a nitrile being included in the pores and the voids asa guest compound (A), and

-   -   the ratio of the amount of the guest compound (A) present in the        pores and the voids to the total amount of the guest compound        included in the pores and the voids being 60 mol % or more.        [2] The polymer-metal complex crystal including a guest compound        according to [1], wherein the guest compound (A) is an alicyclic        hydrocarbon having 3 to 20 carbon atoms or an aromatic        hydrocarbon having 6 to 10 carbon atoms.        [3] The polymer-metal complex crystal including a guest compound        according to [1] or [2], wherein the guest compound (A) is a        saturated alicyclic hydrocarbon having 3 to 20 carbon atoms.        [4] The polymer-metal complex crystal including a guest compound        according to any one of [1] to [3], wherein the total occupancy        ratio of the guest compound included in the pores and the voids        of the polymer-metal complex is 10% or more.        [5] The method for producing a crystal structure analysis sample        according to any one of [1] to [4], wherein the ligand having        two or more coordinating moieties is an organic ligand having        three or more coordinating moieties, and the metal ion that        serves as the center metal is a cobalt ion or a zinc ion.        [6] The polymer-metal complex crystal including a guest compound        according to any one of [1] to [5], wherein the polymer-metal        complex is a compound represented by [[M(X)₂]₃(L)₂]_(n) (wherein        M is a metal ion, X is a monovalent anion, L is a tridentate        ligand represented by the following formula (1),

wherein Ar is a substituted or unsubstituted trivalent aromatic group,X¹ to X³ are independently a divalent organic group, or a single bondthat directly bonds Ar and Y¹, Y², or Y³, and Y¹ to Y³ are independentlya monovalent organic group having a coordinating moiety, and n is anarbitrary natural number).[7] The polymer-metal complex crystal including a guest compoundaccording to any one of [1] to [6], wherein the metal ion is an ion of ametal among the metals that belong to Groups 8 to 12 in the periodictable.[8] The polymer-metal complex crystal including a guest compoundaccording to any one of [1] to [7], wherein the metal ion is a zinc(II)ion or a cobalt(II) ion.[9] The polymer-metal complex crystal including a guest compoundaccording to any one of [1] to [8], the polymer-metal complex crystalhaving a cubic or cuboidal shape with a side length of 10 to 1000 μm.[10] A method for producing the polymer-metal complex crystal includinga guest compound according to any one of [1] to [9], the methodincluding immersing a polymer-metal complex crystal including acrystallization solvent in the guest compound (A) in a liquid state, oran inert solvent solution that includes the guest compound (A), thepolymer-metal complex crystal including a crystallization solventincluding a polymer-metal complex that includes a ligand having two ormore coordinating moieties, and a metal ion that serves as a centermetal, the polymer-metal complex having a three-dimensional networkstructure that is formed by the metal ion and the ligand that iscoordinated to the metal ion, and having pores and voids that arethree-dimensionally arranged in the three-dimensional network structurein an ordered manner, a crystallization solvent (excluding the guestcompound (A)) being included in the pores and the voids.[11] A method for preparing a crystal structure analysis sample in whicha molecule of an organic compound for which a molecular structure is tobe determined, is arranged in pores and voids of a polymer-metal complexcrystal in an ordered manner, the method including:

-   -   immersing the polymer-metal complex crystal including a guest        compound according to any one of [1] to [9] in a solvent        solution that includes the organic compound.        [12] The method for preparing a crystal structure analysis        sample according to [11], the method including immersing the        polymer-metal complex crystal including a guest compound        according to any one of [1] to [8] in the solvent solution that        includes the organic compound in an amount of 100 μg or less so        that a value A calculated by the following expression (2) is 0.1        to 30,

$\begin{matrix}{A = \frac{b}{a}} & (2)\end{matrix}$where, b is the amount of the organic compound included in the solventsolution, and a is the amount of a substance having a specific gravityof 1 that is required to fill all of the pores and the voids of thepolymer-metal complex crystal with the substance having a specificgravity of 1.[13] The method for preparing a crystal structure analysis sampleaccording to [11] or [12], wherein the concentration of the organiccompound in the solvent solution is 0.001 to 50 μg/μL.[14] The method for preparing a crystal structure analysis sampleaccording to any one of [11] to [13], wherein the organic compound isimpurities included in a compound derived from a natural product, or asynthetic compound.[15] The method for preparing a crystal structure analysis sampleaccording to any one of [11] to [14], the method including volatilizingthe solvent after immersing the polymer-metal complex crystal includinga guest compound in the solvent solution that includes the organiccompound to concentrate the solvent solution.[16] The method for preparing a crystal structure analysis sampleaccording to [15], wherein the volatilization rate of the solvent is 0.1to 1000 μL/24 hours.[17] The method for preparing a crystal structure analysis sampleaccording to [14] or [15], wherein the solvent is volatilized at 0 to180° C.[18] The method for preparing a crystal structure analysis sampleaccording to any one of [11] to [17], wherein the immersing of thepolymer-metal complex crystal including a guest compound in the solventsolution that includes the organic compound includes immersing one pieceof the polymer-metal complex crystal including a guest compound in thesolvent solution that includes the organic compound.[19] The method for preparing a crystal structure analysis sampleaccording to any one of [11] to [18], the method including:

-   -   a step (I) that separates a mixture that includes an organic        compound for which a molecular structure is to be determined, by        liquid chromatography to obtain a solvent solution of the        organic compound for which the molecular structure is to be        determined; and    -   a step (II) that immerses the polymer-metal complex crystal        including a guest compound according to any one of [1] to [8] in        the solvent solution of the organic compound for which the        molecular structure is to be determined, that has been obtained        in the step (I), and volatilizes the solvent under moderate        conditions to concentrate the solvent solution.        [20] The method for preparing a crystal structure analysis        sample according to any one of [11] to [19], wherein the        molecular structure of the resulting crystal structure analysis        sample can be determined with a resolution of at least 1.5 Å by        applying MoKα radiation (wavelength: 0.71 Å) generated at a tube        voltage of 24 kV and a tube current of 50 mA to the crystal        structure analysis sample, and detecting diffracted X-rays using        a CCD detector.        [21] A method for determining the molecular structure of an        organic compound including analyzing the crystal structure of a        crystal structure analysis sample obtained using the method for        preparing a crystal structure analysis sample according to any        one of [11] to [20] to determine the molecular structure of the        organic compound included in the pores and the voids of the        crystal structure analysis sample.

Advantageous Effects of the Invention

The polymer-metal complex crystal including a guest compound accordingto one aspect of the invention makes it possible to prepare a crystalstructure analysis sample that is useful for determining the molecularstructure of a trace amount of organic compound.

The method for producing a polymer-metal complex crystal including aguest compound according to one aspect of the invention can efficientlyproduce the polymer-metal complex crystal including a guest compoundaccording to one aspect of the invention.

The method for preparing a crystal structure analysis sample accordingto one aspect of the invention can easily and efficiently prepare acrystal structure analysis sample that makes it possible to determinethe molecular structure of an organic compound even when the amount ofthe sample is very small.

The method for determining the molecular structure of an organiccompound according to one aspect of the invention can determine themolecular structure of an organic compound even when the amount ofsample is very small.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a view illustrating the extension direction of a pore formedin a polymer-metal complex.

FIG. 2 is a view illustrating the three-dimensional network structure ofthe polymer-metal complex 1.

FIG. 3 is a view illustrating the three-dimensional network structure ofthe polymer-metal complex 3.

FIG. 4 is a view illustrating the three-dimensional network structure ofthe polymer-metal complex 5.

FIG. 5 is a view illustrating an example of a device used whenconcentrating a solvent solution.

FIG. 6 is a micrograph of a polymer-metal complex crystal includingcyclohexane

FIG. 7 is a view illustrating the polymer-metal complex crystalincluding cyclohexane obtained in Example 1.

FIG. 8 is an enlarged view illustrating the polymer-metal complexcrystal including cyclohexane obtained in Example 1.

FIG. 9 is a view illustrating the polymer-metal complex including2-methyl-1,4-naphthoquinone obtained in Example 9.

FIG. 10 is an enlarged view illustrating the polymer-metal complexincluding 2-methyl-1,4-naphthoquinone obtained in Example 9.

FIG. 11 is a view illustrating the polymer-metal complex including4-cyano-4′-pentylbiphenyl obtained in Example 10.

FIG. 12 is an enlarged view illustrating the polymer-metal complexincluding 4-cyano-4′-pentylbiphenyl obtained in Example 10.

FIG. 13 is a view illustrating a diffraction pattern (Example 11).

FIG. 14 is a view illustrating the polymer-metal complex including1,4-dimethyl-7-isopropylazulene obtained in Example 11.

FIG. 15 is an enlarged view illustrating the polymer-metal complexincluding 1,4-dimethyl-7-isopropylazulene obtained in Example 11.

FIG. 16 is a view illustrating the polymer-metal complex including(3S,3aS,5aS,9bS)-3a,5,5a,9b-tetrahydro-3,5a,9-trimethylnaphtho[1,2-b]furan-2,8(3H,4H)-dioneobtained in Example 12.

FIG. 17 is an enlarged view illustrating the polymer-metal complexincluding(3S,3aS,5aS,9bS)-3a,5,5a,9b-tetrahydro-3,5a,9-trimethylnaphtho[1,2-b]furan-2,8(3H,4H)-dioneobtained in Example 12.

FIG. 18 is a view illustrating the polymer-metal complex including2-(3,4-dimethoxyphenyl)-5,6,7,8-tetramethoxy-4H-1-benzopyran-4-oneobtained in Example 13.

FIG. 19 is an enlarged view illustrating the polymer-metal complexincluding2-(3,4-dimethoxyphenyl)-5,6,7,8-tetramethoxy-4H-1-benzopyran-4-oneobtained in Example 13.

FIG. 20 is a view illustrating the polymer-metal complex including5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one obtainedin Example 14.

FIG. 21 is an enlarged view illustrating the polymer-metal complexincluding 5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-oneobtained in Example 14.

FIG. 22 is a view illustrating the polymer-metal complex including2,2′-bithiophene obtained in Example 16.

FIG. 23 is an enlarged view illustrating the polymer-metal complexincluding 2,2′-bithiophene obtained in Example 16.

FIG. 24 is a view illustrating the polymer-metal complex obtained inComparative Example 1.

FIG. 25 is an enlarged view illustrating the polymer-metal complexobtained in Comparative Example 1.

FIG. 26 is a schematic view illustrating an operation that drops anorganic compound (liquid) for which the molecular structure is to bedetermined, onto a single crystal of a polymer-metal complex including aguest compound using a dropper to prepare a crystal structure analysissample.

FIG. 27 is an enlarged view illustrating the crystal structure analysissample (polymer-metal complex including isoprene) obtained in Example17.

FIG. 28 is an enlarged view illustrating the crystal structure analysissample (polymer-metal complex including cyclohexanone) obtained inExample 17.

DESCRIPTION OF EMBODIMENTS

A polymer-metal complex crystal including a guest compound, a method forproducing a polymer-metal complex crystal including a guest compound, amethod for preparing a crystal structure analysis sample, and a methodfor determining a molecular structure of an organic compound accordingto exemplary embodiments of the invention are described in detail below.

1) Polymer-Metal Complex Crystal Including Guest Compound

A polymer-metal complex crystal including a guest compound according toone embodiment of the invention includes a polymer-metal complex thatincludes a ligand having two or more coordinating moieties, and a metalion that serves as a center metal, the polymer-metal complex having athree-dimensional network structure that is formed by the metal ion andthe ligand that is coordinated to the metal ion, and having pores andvoids (hereinafter may be referred to as “pores and the like”) that arethree-dimensionally arranged in the three-dimensional network structurein an ordered manner, at least one compound selected from the groupconsisting of an aliphatic hydrocarbon, an alicyclic hydrocarbon, anether, an ester, an aromatic hydrocarbon, a halogenated hydrocarbon, anda nitrile being included in the pores and the voids as a guest compound(A), and the ratio of the amount of the guest compound (A) present inthe pores and the voids to the total amount of the guest compoundincluded in the pores and the voids being 60 mol % or more.

(i) Polymer-Metal Complex

The polymer-metal complex used in connection with the embodiments of theinvention has a three-dimensional network structure that includes aligand having two or more coordinating moieties, and a metal ion thatserves as a center metal.

The term “three-dimensional network structure” used herein refers to anetwork-like structure in which a structural unit formed by a ligand(i.e., a ligand having two or more coordinating moieties and anadditional monodentate ligand) and a metal ion that is bonded to theligand is repeatedly arranged three-dimensionally.

Ligand

The ligand having two or more coordinating moieties (hereinafter may bereferred to as “multidentate ligand”) is not particularly limited aslong as the ligand is coordinated to the metal ion to form thethree-dimensional network structure. A known multidentate ligand may beused as the ligand having two or more coordinating moieties.

The term “coordinating moiety” used herein refers to an atom or anatomic group that is included in the ligand, and has an unsharedelectron pair that can form a coordination bond. Examples of thecoordinating moiety include a hetero atom such as a nitrogen atom, anoxygen atom, a sulfur atom, and a phosphorus atom; an atomic group suchas a nitro group, an amino group, a cyano group, and a carboxyl group;and the like. Among these, a nitrogen atom and an atomic group thatincludes a nitrogen atom are preferable.

It is preferable that the multidentate ligand include an aromatic ringsince the planarity of the ligand is improved, and a strongthree-dimensional network structure is easily formed.

It is preferable to use a multidentate ligand having two or morecoordinating moieties, more preferably a multidentate ligand havingthree coordinating moieties (hereinafter may be referred to as“tridentate ligand”), and still more preferably a tridentate ligand inwhich the unshared electron pairs (orbitals) of the three coordinatingmoieties are present in the same plane, and the three coordinatingmoieties are arranged radially with respect to the center of thetridentate ligand at an equal interval.

The expression “present in the same plane” used herein includes a casewhere each unshared electron pair is present in the same plane, and acase where each unshared electron pair is present in a plane that isshifted to some extent (e.g., present in a plane that intersects areference plane at an angle of 20° or less).

The expression “the three coordinating moieties are arranged radiallywith respect to the center of the tridentate ligand at an equalinterval” used herein means that the three coordinating moieties arearranged on lines that extend radially from the center of the ligand atan equal interval, at an almost equal distance from the center of theligand.

Examples of the tridentate ligand include a ligand represented by thefollowing formula (1).

wherein Ar is a substituted or unsubstituted trivalent aromatic group,X¹ to X³ are independently a divalent organic group, or a single bondthat directly bonds Ar and Y¹, Y², or Y³, and Y¹ to Y³ are independentlya monovalent organic group having a coordinating moiety.

Ar in the formula (1) is a trivalent aromatic group.

The number of carbon atoms of Ar is normally 3 to 22, preferably 3 to13, and more preferably 3 to 6.

Examples of Ar include a trivalent aromatic group having a monocyclicstructure that consists of one 6-membered aromatic ring, and a trivalentaromatic group having a fused ring structure in which three 6-memberedaromatic rings are fused.

Examples of the trivalent aromatic group having a monocyclic structurethat consists of one 6-membered aromatic ring include the groupsrespectively represented by the following formulas (2a) to (2d).Examples of the trivalent aromatic group having a fused ring structurein which three 6-membered aromatic rings are fused, include the grouprepresented by the following formula (2e). Note that “*” in the formulas(2a) to (2e) indicates the positions at which X¹ to X³ are bonded.

The aromatic groups represented by the formulas (2a) and (2c) to (2e)may be substituted with a substituent at an arbitrary position. Examplesof a substituent include an alkyl group such as a methyl group, an ethylgroup, an isopropyl group, an n-propyl group, and a t-butyl group; analkoxy group such as a methoxy group, an ethoxy group, an n-propoxygroup, and an n-butoxy group; a halogen atom such as a fluorine atom, achlorine atom, and a bromine atom; and the like. Ar is preferably thearomatic group represented by the formula (2a) or (2b), and particularlypreferably the aromatic group represented by the formula (2b).

X¹ to X³ are independently a divalent organic group, or a single bondthat directly bonds Ar and Y¹, Y², or Y³.

The divalent organic group that may be represented by X¹ to X³ ispreferably a group that can form a pi electron conjugated systemtogether with Ar. When the divalent organic group that may berepresented by X¹ to X³ forms a pi electron conjugated system, theplanarity of the tridentate ligand represented by the formula (1) isimproved, and a strong three-dimensional network structure is easilyformed.

The number of carbon atoms of the divalent organic group is preferably 2to 18, more preferably 2 to 12, and still more preferably 2 to 6.

Examples of the divalent organic group include a divalent unsaturatedaliphatic group having 2 to 10 carbon atoms, a divalent organic grouphaving a monocyclic structure that consists of one 6-membered aromaticring, a divalent organic group having a fused ring structure in whichtwo to four 6-membered aromatic rings are fused, an amide group(—C(═O)—NH—), an ester group (—C(═O)—O—), a combination of two or moredivalent organic groups among these divalent organic groups, and thelike.

Examples of the divalent unsaturated aliphatic group having 2 to 10carbon atoms include a vinylene group, an acetylene group (ethynylenegroup), and the like.

Examples of the divalent organic group having a monocyclic structurethat consists of one 6-membered aromatic ring, include a 1,4-phenylenegroup and the like.

Examples of the divalent organic group having a fused ring structure inwhich two to four 6-membered aromatic rings are fused, include a1,4-naphthylene group, a 1,5-naphthylene group, a 2,6-naphthylene group,an anthracene-1,4-diyl group, and the like.

Examples of a combination of two or more divalent organic groups amongthese divalent organic groups include the groups respectivelyrepresented by the following formulas.

These aromatic rings may include a hetero atom such as a nitrogen atom,an oxygen atom, or a sulfur atom in their ring.

The divalent organic group may be substituted with a substituent.Examples of the substituent include those mentioned above in connectionwith Ar.

The groups respectively represented by the following formulas arepreferable as the divalent organic group that may be represented by X¹to X³.

Y¹ to Y³ are independently a monovalent organic group having acoordinating moiety.

The organic group represented by Y¹ to Y³ is preferably a group that canform a pi electron conjugated system together with Ar and X¹ to X³.

When the organic group represented by Y¹ to Y³ forms a pi electronconjugated system, the planarity of the tridentate ligand represented bythe formula (1) is improved, and a strong three-dimensional networkstructure is easily formed.

The number of carbon atoms of the organic group represented by Y¹ to Y³is preferably 5 to 11, and more preferably 5 to 7.

Examples of the organic group represented by Y¹ to Y³ include theorganic groups respectively represented by the following formulas (3a)to (30. Note that “*” in the formulas (3a) to (3f) indicates theposition at which X¹, X², or X³ is bonded.

The organic groups represented by the formulas (3a) to (3f) may besubstituted with a substituent at an arbitrary position. Examples of thesubstituent include those mentioned above in connection with Ar.

The group represented by the formula (3a) is particularly preferable asY¹ to Y³.

The size of the pores and the like of the polymer-metal complex can beadjusted by appropriately selecting Ar, X¹ to X³, and Y¹ to Y³ in thetridentate ligand represented by the formula (1). The method accordingto one embodiment of the invention makes it possible to efficientlyobtain a single crystal of a polymer-metal complex that has pores andthe like having a size sufficient to include an organic compound forwhich the molecular structure is to be determined.

It is preferable that the tridentate ligand represented by the formula(1) have high planarity and high symmetry, and have a structure in whicha pi-conjugated system extends over the entire ligand, since a strongthree-dimensional network structure is easily formed. Examples of such atridentate ligand include the ligands respectively represented by thefollowing formulas (4a) to (4f).

Among these, 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) represented bythe formula (4a) is particularly preferable as the tridentate ligandrepresented by the formula (1).

Metal Ion

The metal ion that serves as the center metal is not particularlylimited as long as the metal ion forms a coordination bond together withthe multidentate ligand to form the three-dimensional network structure.A known metal ion may be used as the metal ion that serves as the centermetal. It is preferable to use an ion of a metal among the metals thatbelong to Groups 8 to 12 in the periodic table, such as an iron ion, acobalt ion, a nickel ion, a copper ion, a zinc ion, or a silver ion, andmore preferably an ion of a divalent metal among the metals that belongto Groups 8 to 12 in the periodic table. It is particularly preferableto use a zinc(II) ion or a cobalt(II) ion, since a polymer-metal complexhaving large pores and the like can be easily obtained.

Additional Component Included in Polymer-Metal Complex

The polymer-metal complex used in connection with the embodiments of theinvention is normally stabilized due to coordination of a monodentateligand that serves as a counter ion in addition to the neutralmultidentate ligand.

Examples of the monodentate ligand include a monovalent anion such as achloride ion (Cl⁻), a bromide ion (Br⁻), an iodide ion (I−), and athiocyanate ion (SCN⁻).

The polymer-metal complex used in connection with the embodiments of theinvention may include a solvent; an electrically neutral coordinatingcompound such as ammonia, a monoalkylamine, a dialkylamine, atrialkylamine, and ethylenediamine; a framework-forming aromaticcompound (described below); and the like.

The term “framework-forming aromatic compound” used herein refers to anaromatic compound that is restrained within the three-dimensionalnetwork structure due to a bond (other than a coordination bond) orinteraction, and forms part of the framework of a host molecule (i.e., acompound in which a guest compound can be incorporated). When thepolymer-metal complex includes the framework-forming aromatic compound,the three-dimensional network structure easily becomes stronger, and maybe further stabilized even in a state in which the polymer-metal complexincludes the molecule of an organic compound for which the molecularstructure is to be determined.

Examples of the framework-forming aromatic compound include a fusedpolycyclic aromatic compound. Examples of the fused polycyclic aromaticcompound include the compounds respectively represented by the followingformulas (5a) to (5i).

Three-Dimensional Network Structure of Polymer-Metal Complex

The polymer-metal complex used in connection with the embodiments of theinvention has the three-dimensional network structure that is formed bythe metal ion and the multidentate ligand that is coordinated to themetal ion, and has the pores and the like that are three-dimensionallyarranged in the three-dimensional network structure in an orderedmanner.

The expression “the pores and the like that are three-dimensionallyarranged in the three-dimensional network structure in an orderedmanner” means that the pores and the like are arranged in thethree-dimensional network structure in an ordered manner to such anextent that the pores and the like can be observed by X-ray singlecrystal structure analysis.

The term “pore” used herein refers to a space defined by thethree-dimensional network structure of the polymer-metal complex, suchas spaces A and B (see (a) and (b) in FIG. 3) that are defined by thethree-dimensional network structure, and a space (white area) (see (a)in FIG. 4) that is formed between the repeating units of the sphericalcomplex structure (purple area). The term “void” used herein refers toan internal space of the spherical complex structure, such as therepeating unit (an area enclosed by the red line (see (b) in FIG. 4) ofthe spherical complex structure (see (a) in FIG. 4).

Note that the expressions “pores formed in the three-dimensional networkstructure”, “pores of the polymer-metal complex”, and “pores formed inthe single crystal” used herein have the same meaning.

The three-dimensional network structure is not particularly limited aslong as the three-dimensional network structure has the above structuralfeatures, and the pores and the like have a size sufficient to includethe molecule of an organic compound for which the molecular structure isto be determined.

A polymer-metal complex having relatively large pores and the like isnormally obtained when a multidentate ligand is used in which thedistance from the center of the ligand to the coordinating moiety islong, and a polymer-metal complex having relatively small pores and thelike is normally obtained when a multidentate ligand is used in whichthe distance from the center of the ligand to the coordinating moiety isshort.

The size of the pore has a correlation with the diameter of a circlethat is inscribed to the pore (hereinafter may be referred to as “poreinscribed circle”) in a plane parallel to the crystal plane that isclosest to a perpendicular plane with respect to the extension directionof the pore (hereinafter may be referred to as “parallel plane”).

The extension direction of the pore may be determined by the followingmethod.

Specifically, a crystal plane X (e.g., plane A, plane B, plane C, ordiagonal plane thereof) in an appropriate direction that intersects thetarget pore is selected. The atoms that are present in the crystal planeX and included in the host molecule are represented using the van derWaals radius to draw a cross-sectional view of the pore taken along thecrystal plane X. Likewise, a cross-sectional view of the pore takenalong a crystal plane Y that is shifted from the crystal plane X by oneunit cell is drawn. The center of the cross-sectional shape of the porein the crystal plane X and the center of the cross-sectional shape ofthe pore in the crystal plane Y are connected using a straight line(dash-dotted line) (see FIG. 1). The direction of the straight linecorresponds to the extension direction of the pore.

The diameter of the pore inscribed circle may be determined by thefollowing method.

Specifically, a cross-sectional view of the pore taken along theparallel plane is drawn in the same manner as described above. The poreinscribed circle is drawn using the cross-sectional view, and thediameter of the pore inscribed circle is measured. The measured value isconverted into the actual scale to determine the actual diameter of thepore inscribed circle.

The diameter of the pore inscribed circle in each parallel plane ismeasured while gradually shifting the parallel plane in parallel by oneunit cell to determine the diameter of the smallest inscribed circle andthe diameter of the largest inscribed circle.

The diameter of the pore inscribed circle of the polymer-metal complexused in connection with the embodiments of the invention is preferably 2to 30 Å, and more preferably 3 to 10 Å.

When the shape of the pore significantly differs from a true circle, itis preferable to predict the guest molecule inclusion capability of thepolymer-metal complex from the minor axis and the major axis of the poreinscribed ellipse in the parallel plane.

The major axis of the pore inscribed ellipse of the polymer-metalcomplex used in connection with the embodiments of the invention ispreferably 2 to 30 Å, and more preferably 3 to 10 Å. The minor axis ofthe pore inscribed ellipse of the polymer-metal complex used inconnection with the embodiments of the invention is preferably 2 to 30Å, and more preferably 3 to 10 Å.

The pore volume in the polymer-metal complex used in connection with theembodiments of the invention may be calculated using the methoddescribed in Acta Crystallogr. A46, 194-201 (1990). Specifically, thepore volume in the polymer-metal complex may be calculated using theexpression “volume of single crystal×void ratio in unit cell” based onthe solvent accessible void (void volume in unit cell) calculated by acalculation program “PLATON SQUEEZE PROGRAM”.

The pore volume (i.e., the total pore volume in one piece of the singlecrystal) in the polymer-metal complex used in connection with theembodiments of the invention is preferably 1×10⁻⁷ to 0.1 mm³, and morepreferably 1×10⁻⁵ to 1×10⁻³ mm³.

When the polymer-metal complex includes the repeating units of thespherical complex structure, each spherical complex structure has aninternal space (void). The size of the void may be calculated using themethod described in Acta Crystallogr. A46, 194-201 (1990) in the samemanner as the pore volume.

It is preferable that the polymer-metal complex used in connection withthe embodiments of the invention does not lose crystallinity, and haverelatively large pores and the like even after the guest compound hasbeen introduced into (incorporated in) the pores and the like.

The polymer-metal complex includes an organic solvent (hereinafter maybe referred to as “crystallization solvent”) used when synthesizing thepolymer-metal complex in the pores and the like.

When the crystallization solvent is the guest compound (A), theresulting polymer-metal complex corresponds to the polymer-metal complexincluding a guest compound according to one embodiment of the invention.

When the crystallization solvent is not the guest compound (A), thecrystallization solvent is replaced with the guest compound (A) asdescribed later to obtain a polymer-metal complex including a guestcompound that may suitably be used to prepare a crystal structureanalysis sample.

The polymer-metal complex used in connection with the embodiments of theinvention is normally obtained by mixing a first solvent solution of theligand having two or more coordinating moieties and a second solventsolution that includes a metal salt so that the resulting polymer-metalcomplex includes the ligand and the metal ion in a given ratio. Forexample, the tridentate ligand represented by the formula (1) may beused as the ligand, and a zinc(II) salt such as zinc iodide or zincbromide, a cobalt(II) salt such as cobalt thiocyanate, or the like maybe used as the metal salt. Note that the details of the method forsynthesizing the polymer-metal complex are described later.

Specific examples of the polymer-metal complex used in connection withthe embodiments of the invention include polymer-metal complexesrespectively represented by the following formulas (6a) to (6d) that areobtained using TPT respectively by the formula (4a) as the tridentateligand. These polymer-metal complexes are particularly suitable as thepolymer-metal complex used in connection with the embodiments of theinvention.[(ZnI₂)₃(TPT)₂(solv)_(a)]_(b)  (6a)[(ZnBr₂)₃(TPT)₂(solv)_(a)]_(b)  (6b)[(ZnI₂)₃(TPT)₂(SA)(solv)_(a))]_(b)  (6c)[(Co(NCS)₂)₃(TPT)₄(solv)_(a)]_(b)  (6d)wherein “solv” is the crystallization solvent included in the pores andthe like, “SA” is the framework-forming aromatic compound, and a and bare an arbitrary natural number.

These polymer-metal complexes are described in detail below. Note thatthe ligand and the solvent molecule may be hereinafter abbreviated asshown below.

PhNO₂: nitrobenzene

TPH: triphenylene

PER: perylene

MeOH: methanol

DCB: 1,2-dichlorobenzene(1) [(ZnI₂)₃(TPT)₂(solv)_(a)]_(b)  (6a)

Examples of the polymer-metal complex represented by the formula (6a)include [(ZnI₂)₃(TPT)₂(PhNO₂)_(5.5)]_(n) (polymer-metal complex 1)disclosed in JP-A-2008-214584 and J. Am. Chem. Soc. 2004, v. 126, pp.16292-16293.

FIG. 2 (see (a) to (d)) illustrates the three-dimensional networkstructure of the polymer-metal complex 1.

The three-dimensional network structure of the polymer-metal complex 1includes three-dimensional network structures 1a and 1b. In thethree-dimensional network structures 1a and 1b, the pyridyl groups oftwo TPT and two iodide ions are coordinated to each zinc(II) ion to forma tetra-coordinated tetrahedral structure. The structures including thezinc(II) ion are three-dimensionally connected by TPT to form eachthree-dimensional network structure (see (a) in FIG. 2).

The three-dimensional network structures 1a and 1b have a closed cyclicchain structure that consists of ten TPT molecules and ten Zn atoms asthe shortest closed cyclic chain structure (see (b) in FIG. 2).

The three-dimensional network structures 1a and 1b are considered to bea helical hexagonal three-dimensional network structure in which thepitch along the (010) axis is 15 Å (see (c) in FIG. 2).

The three-dimensional network structures 1a and 1b do not share anidentical zinc(II) ion, and are independent of each other. Thethree-dimensional network structures 1a and 1b penetrate each other in acomplex nested form so as to share an identical space to form acomposite three-dimensional network structure.

The polymer-metal complex 1 having the composite three-dimensionalnetwork structure has identical pores that are arranged in an orderedmanner (see (d) in FIG. 2).

The void ratio of the polymer-metal complex 1 is 50%.

The diameter of the pore inscribed circle of the polymer-metal complex 1is 5 to 8 Å.(2) [(ZnBr₂)₃(TPT)₂(solv)_(a)]_(b)  (6b)

Examples of the polymer-metal complex represented by the formula (6b)include [(ZnBr₂)₃(TPT)₂(PhNO₂)₅(H₂O)]_(n) (polymer-metal complex 2)disclosed in JP-A-2008-214318.

The polymer-metal complex 2 has the same three-dimensional networkstructure as that of the polymer-metal complex 1, except that (ZnI₂) isreplaced with (ZnBr₂).

The pore shape, the pore size, and the void ratio of the polymer-metalcomplex 2 are almost the same as those of the polymer-metal complex 1.(3) [(ZnI₂)₃(TPT)₂(SA)(solv)_(a))]_(b)  (6c)

Examples of the polymer-metal complex represented by the formula (6c)include [(ZnI₂)₃(TPT)₂(TPH)(PhNO₂)_(3.9)(MeOH)_(1.8)]_(n) (polymer-metalcomplex 3) and [(ZnI₂)₃(TPT)₂(PER)(PhNO₂)₄]_(n) (polymer-metal complex4) disclosed in JP-A-2006-188560.

FIG. 3 (see (a) to (c)) illustrates the three-dimensional networkstructure of the polymer-metal complex 3.

The three-dimensional network structure of the polymer-metal complex 3includes three-dimensional network structures 1A and 1B. In thethree-dimensional network structures 1A and 1A, two iodide ions and thepyridyl groups of two TPT are coordinated to each zinc(II) ion to form atetra-coordinated tetrahedral structure. The structures including thezinc(II) ion are three-dimensionally connected by TPT to form eachthree-dimensional network structure.

The three-dimensional network structures 1A and 1B do not share anidentical zinc(II) ion, and are independent of each other. Thethree-dimensional network structures 1A and 1B penetrate each other in acomplex nested form so as to share an identical space to form acomposite three-dimensional network structure.

The triphenylene molecule (2) included in the polymer-metal complex 3 isfirmly intercalated between the pi plane of tris(4-pyridyl)triazine (TPT(1a)) of the three-dimensional network structure 1A and the pi plane oftris(4-pyridyl)triazine (TPT (1b)) of the three-dimensional networkstructure 1B (see (b) in FIG. 3). The triphenylene molecule isstabilized by the pi-pi interaction between TPT (1a) and TPT (1b), andserves as part of the main framework of the polymer-metal complex 3. InFIG. 3, (b) is a side view of the area enclosed in (a).

The polymer-metal complex 3 has two types of pores (pores A and B) thatare arranged in the three-dimensional network structure in an orderedmanner (see (c) in FIG. 3). The pores A and B are formed in an orderedmanner in a laminate structure in which TPT and TPH are alternatelystacked.

The pore A has an approximately cylindrical shape, and is almostcompletely surrounded by the hydrogen atoms present at the side edge ofthe pi planes of a number of TPT and TPH that are stacked.

The pore B is approximately in the shape of a triangular prism. Twosides among the three sides of the triangular prism are surrounded bythe pi planes of TPT, and the remaining side is surrounded by thehydrogen atoms present at the side edge of the pi planes of a number ofTPT and TPH that are stacked.

The pores A and B have an elongated shape that meanders to some extent.

The void ratio of the polymer-metal complex 3 is 28%.

The diameter of the circle inscribed to the pore A of the polymer-metalcomplex 3 is 5 to 8 Å.

The diameter of the circle inscribed to the pore B of the polymer-metalcomplex 3 is 5 to 8 Å.

The polymer-metal complex 4 has the same framework structure as that ofthe polymer-metal complex 3, except that the perylene molecule isintercalated between two TPT instead of the triphenylene molecule.

The pore shape, the pore size, and the void ratio of the polymer-metalcomplex 4 are almost the same as those of the polymer-metal complex 3.(4) [(Co(NCS)₂)₃(TPT)₄(solv)_(a)]_(b)  (6d)

Examples of the polymer-metal complex represented by the formula (6d)include [(Co(NCS)₂)₃(TPT)₄(DCB)₂₅(MeOH)₅]_(n) (polymer-metal complex 5)disclosed in WO2011/062260.

FIG. 4 (see (a)) illustrates the three-dimensional network structure ofthe polymer-metal complex 5.

The polymer-metal complex 5 has a (Co₆(TPT)₄) structure that consists ofsix cobalt ions and four TPT as a structural unit. The structural unithas an octahedral shape, wherein a cobalt ion is situated at each vertexof the octahedron (see (b) in FIG. 4). The pyridyl groups of four TPTand two thiocyanate ions are coordinated to each cobalt(II) ion to forma hexa-coordinated octahedral structure. In FIG. 4, (b) is an enlargedview of the area enclosed in (a).

The (Co₆(TPT)₄) structure are three-dimensionally connected so as toshare the cobalt ion situated at each vertex of the (Co₆(TPT)₄)structure to form pores between the (Co₆(TPT)₄) structures (see (c) inFIG. 4).

The structural unit has a void therein.

The void ratio of the polymer-metal complex 5 is 78%. This value iscalculated using the total volume of the pores and the like.

The diameter of the pore inscribed circle of the polymer-metal complex 5is 10 to 18 Å.

It is preferable that the polymer-metal complex crystal including aguest compound according to one embodiment of the invention does nothinder introduction (incorporation) of the desired organic compound intothe pores and the like, and be designed so that the guest compound (A)included in the pores and the like is replaced with the desired organiccompound to form a polymer-metal complex crystal including an organiccompound.

At least one compound selected from the group consisting of an aliphatichydrocarbon, an alicyclic hydrocarbon, an ether, an ester, an aromatichydrocarbon, a halogenated hydrocarbon, and a nitrile is preferable asthe guest compound (A) from the above point of view.

The aliphatic hydrocarbon that may be used as the guest compound (A) isnot particularly limited as long as the aliphatic hydrocarbon can enterthe pores and the like. Examples of the aliphatic hydrocarbon that maybe used as the guest compound (A) include a linear or branched saturatedaliphatic hydrocarbon having 1 to 20 carbon atoms, such as methane,ethane, propane, butane, pentane, hexane, heptane, octane, decane,tetradecane, and octadecane; a linear or branched unsaturated aliphatichydrocarbon having 2 to 20 carbon atoms that includes one or two or moredouble bonds or triple bonds in the molecule; and the like.

The alicyclic hydrocarbon is not particularly limited as long as thealicyclic hydrocarbon can enter the pores and the like. Examples of thealicyclic hydrocarbon include a saturated alicyclic hydrocarbon having 3to 20 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane,cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane,cyclododecane, cycloundecane, and decalin; an unsaturated alicyclichydrocarbon having 3 to 20 carbon atoms that is derived from thesecompounds, and has one or two or more double bonds or triple bonds inthe molecule; and the like.

The ether is not particularly limited as long as the ether can enter thepores and the like. Examples of the ether include dimethyl ether,diethyl ether, dipropyl ether, dibutyl ether, t-butyl ether, dihexylether, methylethyl ether, tetrahydrofuran, 1,2-dimethoxyethane,1,4-dioxane, and the like.

The ester is not particularly limited as long as the ester can enter thepores and the like. Examples of the ester include ethyl formate, methylacetate, ethyl acetate, propyl acetate, pentyl acetate, octyl acetate,ethyl lactate, ethyl propionate, methyl butanoate, ethyl butanoate,pentyl butanoate, pentyl valerate, and the like.

The aromatic hydrocarbon is not particularly limited as long as thearomatic hydrocarbon can enter the pores and the like. Examples of thearomatic hydrocarbon include benzene, toluene, xylene, mesitylene,naphthalene, anthracene, phenanthrene, and the like.

The halogenated hydrocarbon is not particularly limited as long as thehalogenated hydrocarbon can enter the pores and the like. Examples ofthe halogenated hydrocarbon include the compounds mentioned above inconnection with the aliphatic hydrocarbon, the alicyclic hydrocarbon,and the aromatic hydrocarbon, in which one or two or more carbon atomsare substituted with a halogen atom such as a fluorine atom, a chlorineatom, a bromine atom, or an iodine atom. Specific examples of thehalogenated hydrocarbon include dichloromethane, chloroform, carbontetrachloride, 1,2-dichloroethane, trifluoromethane, chlorobenzene,bromobenzene, 1,2-dichlorobenzene, and the like.

The nitrile is not particularly limited as long as the nitrile can enterthe pores and the like. Examples of the nitrile include acetonitrile,benzonitrile, and the like.

These compounds may be used either alone or in combination.

Among these, an alicyclic hydrocarbon having 3 to 20 carbon atoms and anaromatic hydrocarbon having 6 to 10 carbon atoms are preferable, analicyclic hydrocarbon having 5 to 10 carbon atoms and an aromatichydrocarbon having 6 to 10 carbon atoms are more preferable, cyclohexaneand toluene are still more preferable, and cyclohexane is particularlypreferable, since replacement with an organic compound can be easilyachieved, and a high-quality crystal structure analysis sample can beeasily prepared.

The ratio of the amount of the guest compound (A) present in thepolymer-metal complex to the total amount of the guest compound includedin the pores and the like is 60 mol % or more, preferably 75 mol % ormore, and more preferably 90 mol % or more.

If the ratio of the amount of the guest compound (A) present in thepolymer-metal complex to the total amount of the guest compound includedin the pores and the like is less than 60 mol %, it may be difficult toeasily prepare the target crystal structure analysis sample.

In the polymer-metal complex crystal including a guest compoundaccording to one embodiment of the invention, the total occupancy ratioof the guest compound included in the pores and the voids of thepolymer-metal complex is preferably 10% or more, more preferably 30% ormore, and still more preferably 50% or more.

If the occupancy ratio is less than 10%, it may be impossible or verydifficult to determine the structure of the guest compound by X-raysingle crystal structure analysis, and the resulting structural data mayhave low chemical reliability.

The term “occupancy ratio” used herein refers to a value obtained bysingle crystal structure analysis, and represents the amount of guestcompound actually present in the single crystal provided that the amountof guest compound in an ideal inclusion state is 100%.

2) Method for Producing Polymer-Metal Complex Crystal Including GuestCompound

A method for producing a polymer-metal complex crystal including a guestcompound (hereinafter may be referred to as “production method”)according to one embodiment of the invention includes immersing apolymer-metal complex crystal including a crystallization solvent in theguest compound (A) in a liquid state, or an inert solvent solution thatincludes the guest compound (A), the polymer-metal complex crystalincluding a crystallization solvent including a polymer-metal complexthat includes a ligand having two or more coordinating moieties, and ametal ion that serves as a center metal, the polymer-metal complexhaving a three-dimensional network structure that is formed by the metalion and the ligand that is coordinated to the metal ion, and havingpores and the like that are three-dimensionally arranged in thethree-dimensional network structure in an ordered manner, acrystallization solvent (excluding the guest compound (A), hereinafterthe same) being included in the pores and the like.

Specifically, the production method according to one embodiment of theinvention includes (i) synthesizing a polymer-metal complex crystal in acrystallization solvent to obtain a polymer-metal complex crystalincluding a crystallization solvent, and (ii) immersing thepolymer-metal complex crystal including the crystallization solvent inthe guest compound (A) in a liquid state, or an inert solvent solutionthat includes the guest compound (A), to replace the crystallizationsolvent included in the pores and the like with the guest compound (A).

(i) Synthesis of Polymer-Metal Complex Crystal Including CrystallizationSolvent

The polymer-metal complex including a crystallization solvent used inconnection with one embodiment of the invention may be synthesized usinga known method that reacts a multidentate ligand and a metalion-containing compound, for example. For example, the polymer-metalcomplex including a crystallization solvent may be synthesized by addinga second solvent solution of a metal ion-containing compound to a firstsolvent solution of a multidentate ligand, and allowing the mixture tostand at 0 to 70° C. for several hours to several days.

The metal ion-containing compound is not particularly limited. Examplesof the metal ion-containing compound include a compound represented byMX_(n). Note that M is a metal ion, X is a counter ion, and n is thevalence of M.

Specific examples of X include F⁻, Cl⁻, Br⁻, I⁻, SCN⁻, NO₃ ⁻, ClO₄ ⁻,BF₄ ⁻, SbF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, CH₃CO₂ ⁻, and the like.

It is preferable to use a compound that dissolves the multidentateligand or the like as the first solvent and the second solvent.

Specific examples of such a compound include an aromatic hydrocarbonsuch as benzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene,and nitrobenzene; an aliphatic hydrocarbon such as n-pentane, n-hexane,and n-heptane; an alicyclic hydrocarbon such as cyclopentane,cyclohexane, and cycloheptane; a nitrile such as acetonitrile andbenzonitrile; a sulfoxide such as dimethyl sulfoxide (DMSO); an amidesuch as N,N-dimethylformamide and N-methylpyrrolidone; an ether such asdiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; analcohol such as methanol, ethanol, and isopropyl alcohol; a ketone suchas acetone, methyl ethyl ketone, and cyclohexanone; a cellosolve such asethylcellosolve; a halogenated hydrocarbon such as dichloromethane,chloroform, carbon tetrachloride, and 1,2-dichloroethane; an ester suchas methyl acetate, ethyl acetate, ethyl lactate, and ethyl propionate;water; and the like. These solvents may be used either alone or incombination.

When it is desired to obtain a relatively large single crystal of thepolymer-metal complex, it is preferable that the first solvent and thesecond solvent be immiscible with each other (i.e., be separated intotwo layers). Specifically, it is preferable to use nitrobenzene,dichlorobenzene, nitrobenzene, or a mixed solvent thereof with methanolas the first solvent, and use an alcohol such as methanol, ethanol, orisopropyl alcohol as the second solvent.

The polymer-metal complexes 1 to 5 can be synthesized using the methodsdescribed in the above documents.

(ii) Replacement with Guest Compound

The resulting polymer-metal complex has a three-dimensional networkstructure, and has pores and the like that are three-dimensionallyarranged in the three-dimensional network structure in an orderedmanner, and the crystallization solvent is included in the pores and thelike.

The target polymer-metal complex crystal including a guest compound canbe obtained by immersing the polymer-metal complex crystal including acrystallization solvent in the guest compound (A) in a liquid state, oran inert solvent solution that includes the guest compound (A), toreplace the crystallization solvent included in the pores and the likewith the guest compound (A).

Examples of the guest compound (A) include those mentioned above.

The inert solvent is not particularly limited as long as the inertsolvent is miscible with the guest compound (A), and inert to thepolymer-metal complex (i.e., does not easily replace the crystallizationsolvent included in the pores and the like of the polymer-metal complexas compared with the guest compound (A)). Examples of the inert solventinclude an alcohol such as methanol, ethanol, and isopropyl alcohol.

When the guest compound (A) is liquid, the guest compound (A) may beused directly.

The guest compound (A) in a liquid state, or the inert solvent solutionthat includes the guest compound (A) (hereinafter may be referred to as“solution of the guest compound (A)”) is normally used in an amount of 1to 100 mL, and preferably 5 to 30 mL, based on 100 mg of thepolymer-metal complex crystal.

The immersion temperature is not particularly limited, but is normally 0to 70° C., preferably 10 to 70° C., and more preferably 20 to 60° C.

The immersion time is determined so that 60% or more of the pores andthe like are occupied by the guest compound (A). The immersion time isnormally 6 hours or more, preferably 12 hours to 10 days, and morepreferably 1 to 8 days.

It is preferable to remove the supernatant liquid of the immersionliquid (i.e., the solution of the guest compound (A)) by decantationabout every other day, and add the immersion liquid in amount equal tothe amount of the supernatant liquid that has been removed, in order topromote replacement with the guest compound (A).

Whether or not the guest compound (A) is included in the pores and thelike may be determined by elemental analysis, X-ray crystal structureanalysis, and the like.

Since the polymer-metal complex crystal including a guest compoundobtained as described above is designed so that the guest compound (A)included in the pores and the like is easily replaced with a traceamount of organic compound sample, the polymer-metal complex crystalincluding a guest compound is useful as a material for preparing acrystal structure analysis sample described later.

The polymer-metal complex crystal including a guest compound obtained asdescribed above makes it possible to efficiently introduce (incorporate)various other guest compounds without hindering guest replacement. Thesample used for guest replacement need not be a crystalline solid, andmay be a liquid, a gas, a noncrystalline solid, or the like. The amountof the guest compound necessary for inclusion may be 5 μg or less. GoodX-ray single crystal structure analysis data can be obtained even whenthe amount of the guest compound is several tens of nanograms. X-raysingle crystal structure analysis that utilizes the embodiments of theinvention can accurately determine a steric structure including theabsolute configuration of a molecule. It is also possible to determinethe steric structure (absolute structure) of an unstable compound thateasily undergoes thermal decomposition or solvolysis without heating thecompound, or dissolving the compound in a solvent, a buffer, or thelike.

It is preferable that the polymer-metal complex crystal including aguest compound according to one embodiment of the invention be a singlecrystal having a cubic or cuboidal shape with a side length of 10 to1000 μm, and preferably 60 to 200 μm. A high-quality crystal structureanalysis sample can be easily obtained by utilizing the single crystalof the polymer-metal complex having such a shape.

It is preferable that the single crystal of the polymer-metal complexincluding a guest compound according to one embodiment of the inventionbe designed so that the molecular structure of the resulting crystalstructure analysis sample can be determined with a resolution of atleast 1.5 Å by applying MoKα radiation (wavelength: 0.71 Å) generated ata tube voltage of 24 kV and a tube current of 50 mA to the crystalstructure analysis sample, and detecting diffracted X-rays using a CCDdetector. A high-quality crystal structure analysis sample can beobtained by utilizing the single crystal of the polymer-metal complexhaving the above properties.

3) Method for Producing Crystal Structure Analysis Sample

A method for preparing a crystal structure analysis sample according toone embodiment of the invention prepares a crystal structure analysissample in which the molecules of an organic compound for which themolecular structure is to be determined, are arranged in pores and thelike of a polymer-metal complex crystal in an ordered manner, andincludes immersing the polymer-metal complex crystal including a guestcompound according to one embodiment of the invention in a solventsolution that includes the organic compound.

Organic Compound for which Molecular Structure is Determined

The organic compound for which the molecular structure is to bedetermined (hereinafter may be referred to as “organic compound (a)”) isnot particularly limited as long as the organic compound has a size thatallows the organic compound to enter the pores and the like of thepolymer-metal complex.

The organic compound (a) is a low-molecular-weight compound, themolecular weight of the organic compound (a) is normally 20 to 3000, andpreferably 100 to 500.

When the organic compound (a) is a chain-like polymer compound (e.g.,polyethylene) that includes a repeating unit, the molecular weight ofthe organic compound (a) is normally 10³ to 10⁶, and preferably 10⁴ to10⁵. The organic compound (a) may be either solid or liquid at aboutroom temperature (about 25° C.).

It is preferable to roughly determine the size of the organic compound(a) in advance by nuclear magnetic resonance spectroscopy, massspectrometry, elemental analysis, or the like, and appropriately selectthe polymer-metal complex crystal including a guest compoundcorresponding to the size of the organic compound (a).

When the organic compound (a) is impurities included in a syntheticcompound (e.g., a compound derived from a natural product, agriculturalchemical, medicine, or synthetic polymer), it is preferable to increasethe purity of the organic compound (a) using a known purification methodsuch as liquid chromatography, and then prepare the crystal structureanalysis sample using the method according to one embodiment of theinvention. When using liquid chromatography, the eluant that includesthe target product may be used directly as the solvent solution of theorganic compound described later.

The method for preparing a crystal structure analysis sample accordingto one embodiment of the invention can prepare the crystal structureanalysis sample without requiring a large amount of the organic compound(α), and is useful when only a trace amount of the organic compound (α)is available (e.g., when the organic compound (α) is impurities includedin a compound derived from a natural product, an agricultural chemical,or a medicine). The organic compound (α) may be either solid or liquidat room temperature (20° C.).

The amount of the organic compound (α) included in the solvent solutionis not particularly limited, and may be 100 μg or less. The lower limitof the amount of the organic compound (α) included in the solventsolution is normally 0.5 μg or more.

It is preferable that the method for preparing a crystal structureanalysis sample according to one embodiment of the invention includeimmersing the single crystal of the polymer-metal complex including aguest compound in the solvent solution that includes the organiccompound in an amount of 100 μg or less so that a value A calculated bythe following expression (2) is 100 or less, preferably 0.1 to 30, andmore preferably 1 to 5.

$\begin{matrix}{A = \frac{b}{a}} & (2)\end{matrix}$where, b is the amount of the organic compound included in the solventsolution, and a is the amount of a substance having a specific gravityof 1 that is required to fill all of the pores and the like of thepolymer-metal complex crystal with the substance having a specificgravity of 1.

When the value A is 0.1 to 30, the organic compound (α) is sufficientlyintroduced into the pores and the like of the single crystal of thepolymer-metal complex, and a high-quality crystal structure analysissample is easily obtained. The target crystal structure analysis samplecan be obtained even when the value A is large. However, a furtherimprovement in effects may not be achieved, and the organic compound (α)may be wasted. Specifically, the method according to one embodiment ofthe invention is useful when preparing a crystal structure analysissample for determining the structure of an organic compound that isavailable in an only trace amount (e.g., impurities included in acompound derived from a natural product, an agricultural chemical, or amedicine).

Note that the organic compound (α) need not necessarily be included inall of the pores and the likes of the polymer-metal complex. It ispossible to prepare a high-quality crystal structure analysis sampleeven when the value A is smaller than 1.

The concentration of the organic compound (α) in the solvent solution isnot particularly limited. The concentration of the organic compound (α)in the solvent solution is normally 0.001 to 50 μg/μL, preferably 0.01to 5 μg/μL, and more preferably 0.1 to 1 μg/μL, from the viewpoint ofefficiently preparing a high-quality crystal structure analysis sample.

The solvent used to prepare the solvent solution is not particularlylimited as long as the solvent does not dissolve the crystal of thepolymer-metal complex, and dissolves the organic compound (α), and thesolvent solution of the organic compound (α) can be concentrated byvolatilizing the solvent from the solvent solution of the organiccompound (α).

It is preferable to use a solvent having a boiling point at normalpressure (1×10⁵ Pa) of 0 to 250° C., more preferably 0 to 185° C., andstill more preferably 30 to 150° C.

Specific examples of the solvent include an aromatic hydrocarbon such asbenzene, toluene, xylene, chlorobenzene, and 1,2-dichlorobenzene; analiphatic hydrocarbon such as n-pentane, n-hexane, and n-heptane; analicyclic hydrocarbon such as cyclopentane, cyclohexane, andcycloheptane; a nitrile such as acetonitrile and benzonitrile; asulfoxide such as dimethyl sulfoxide; an amide such asN,N-dimethylformamide and N-methylpyrrolidone; an ether such as diethylether, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; an alcoholsuch as methanol, ethanol, and isopropyl alcohol; a ketone such asacetone, methyl ethyl ketone, and cyclohexanone; a cellosolve such asethylcellosolve; a halogenated hydrocarbon such as dichloromethane,chloroform, carbon tetrachloride, and 1,2-dichloroethane; an ester suchas methyl acetate, ethyl acetate, ethyl lactate, and ethyl propionate;water; and the like. These solvents may be used either alone or incombination.

It is preferable to use the guest compound (A) as the solvent since ahigh-quality crystal structure analysis sample can be obtained.

When implementing the method for preparing a crystal structure analysissample according to one embodiment of the invention, the polymer-metalcomplex crystal including a guest compound according to one embodimentof the invention is immersed in the solvent solution that includes theorganic compound (α).

The number of single crystals of the polymer-metal complex including aguest compound to be immersed in the solvent solution is notparticularly limited as long as the requirement relating to the value Ais satisfied. When the amount of the organic compound (α) is very small,the target crystal structure analysis sample can be obtained byimmersing one single crystal. When the amount of the organic compound(α) is large, two or more single crystals of an identical polymer-metalcomplex including a guest compound may be immersed in the solventsolution, or single crystals of different polymer-metal complexesincluding a guest compound may be immersed in the solvent solution atthe same time.

When implementing the method for preparing a crystal structure analysissample according to one embodiment of the invention, the solvent isvolatilized under moderate conditions after immersing the single crystalof the polymer-metal complex including a guest compound in the solventsolution to concentrate the solvent solution. This makes it possible toefficiently introduce a trace amount of the organic compound (α) intothe pores and the like of the single crystal.

The immersion conditions (concentration conditions) are not particularlylimited. The temperature of the solvent is preferably 0 to 180° C., morepreferably 0 to 80° C., and still more preferably 20 to 60° C.

The immersion time (concentration time) is normally 6 hours or more,preferably 12 to 168 hours, and more preferably 24 to 78 hours.

The volatilization rate of the solvent is preferably 0.1 to 1000 μL/24hours, more preferably 1 to 100 μL/24 hours, and still more preferably 5to 50 μL/24 hours.

If the volatilization rate of the solvent is to high, it may bedifficult to obtain a high-quality crystal structure analysis sample. Ifthe volatilization rate of the solvent is to low, the work efficiencymay deteriorate.

The temperature employed when volatilizing the solvent is determinedtaking account of the boiling point of the organic solvent, but isnormally 0 to 180° C., preferably 0 to 120° C., and more preferably 15to 60° C.

The operation that volatilizes the solvent after immersing thepolymer-metal complex crystal including a guest compound in the solventsolution that includes the organic compound (α) to concentrate thesolvent solution may be performed under normal pressure, or may beperformed under reduced pressure, or may be performed under pressure.

The pressure employed when performing the operation that volatilizes thesolvent to concentrate the solvent solution is normally 1 to 1×10⁶ Pa,and preferably to 1×10 to 1×10⁶ Pa.

The volatilization rate of the solvent can be appropriately adjusted byadjusting the temperature and the pressure employed when performing theoperation that concentrates the solvent solution.

The method for preparing a crystal structure analysis sample accordingto one embodiment of the invention may include a step (I) that separatesa mixture that includes the organic compound (α) by liquidchromatography to obtain a solvent solution of the organic compound (α),and a step (II) that immerses the single crystal of the polymer-metalcomplex including a guest compound in the solvent solution of theorganic compound (α) that has been obtained in the step (I), andvolatilizes the solvent under moderate conditions to concentrate thesolvent solution.

As illustrated in FIG. 26, a mixture that includes the organic compound(α) is separated using a liquid chromatography device to obtain asolvent solution of the organic compound (α) (i.e., a solution thatincludes the organic compound (α) as an organic compound other than thesolvent), the single crystal of the polymer-metal complex including aguest compound according to one embodiment of the invention is immersedin the solvent solution of the organic compound (α) (fraction A), andthe solvent is volatilized under moderate conditions to concentrate thesolvent solution to obtain a crystal structure analysis sample.

In this case, the solvent of the solvent solution may be replaced withanother solvent, and the crystal of the polymer complex may be immersedin the resulting solution.

According to this method, a crystal structure analysis sample can beprepared by separating a mixture of a plurality of compounds having asimilar structure by liquid chromatography, and immersing the crystal ofthe polymer-metal complex in each of the solvent solutions respectivelyincluding the separated compounds. This method is useful when separatinga mixture of compounds having a similar structure for which it isdifficult to determine the structure of each compound based only on themeasurement data (e.g., NMR spectrum), and determining the molecularstructure of each compound.

The method for preparing a crystal structure analysis sample accordingto one embodiment of the invention can also be applied the case wherethe organic compound (α) is a substance that is liquid at about roomtemperature (about 25° C.). Specifically, the single crystal of thepolymer-metal complex including a guest compound according to oneembodiment of the invention is immersed in the solvent solution of aliquid organic compound (α), and the solvent is volatilized undermoderate conditions to concentrate the solvent solution to prepare acrystal structure analysis sample.

As illustrated in FIG. 26, a trace amount of a liquid organic compound(α) may be dropped onto the single crystal of the polymer-metal complexincluding a guest compound according to one embodiment of the inventionusing a dropper or the like, and the single crystal may be allowed tostand at room temperature (25° C.) for several hours to several days toprepare a crystal structure analysis sample. When the organic compound(α) is volatile at about room temperature (25° C.), it is preferable toplace the sample obtained by dropping the organic compound (α) onto thesingle crystal of the polymer-metal complex including a guest compoundin an airtight container such as a vial.

It is preferable that the molecular structure of the resulting crystalstructure analysis sample (single crystal of a polymer-metal complexincluding an organic compound) can be determined with a resolution of atleast 1.5 Å by applying MoKα radiation (wavelength: 0.71 Å) generated ata tube voltage of 24 kV and a tube current of 50 mA to the crystalstructure analysis sample, and detecting diffracted X-rays using a CCDdetector.

A crystal structure analysis sample obtained using the method accordingto one embodiment of the invention has a configuration in which themolecules of the organic compound (α) that has replaced the guestcompound (A) are arranged in the pores and the like of the singlecrystal of the polymer-metal complex in an ordered manner.

The expression “the molecules of the organic compound are arranged in anordered manner” means that the molecules of the organic compound areincluded in the pores and the like of the polymer-metal complex in anordered manner to such an extent that the structure of the organiccompound can be determined by X-ray single crystal structure analysis.

In the crystal structure analysis sample obtained using the methodaccording to one embodiment of the invention, the organic compound (α)need not necessarily be included in all of the pores and the like of thesingle crystal of the polymer-metal complex as long as the structure ofthe organic compound (α) can be determined. For example, the solventused for the solvent solution of the organic compound (α) may beincluded in some of the pores and the like of the single crystal of thepolymer-metal complex.

It is preferable that the occupancy ratio of the molecules of theorganic compound in the crystal structure analysis sample obtained usingthe method according to one embodiment of the invention be 10% or more.The occupancy ratio of the molecules of the organic compound refers to avalue obtained by single crystal structure analysis, and represents theamount of guest molecules actually present in the single crystalprovided that the amount of guest molecules (organic compound (α)) in anideal inclusion state is 100%.

It is possible to efficiently prepare a crystal structure analysissample by satisfying the requirement relating to the value A, selectingthe crystal of the polymer-metal complex having pores and the like thatare appropriate for the size of the molecule of the organic compound(α), and introducing the organic compound (α) into the pores and thelike of the single crystal of the polymer-metal complex having goodquality.

When volatilizing the solvent after immersing the single crystal of thepolymer-metal complex including a guest compound in the solvent solutionof the organic compound (α) to concentrate the solvent solution, thepreparation device A or the preparation device B illustrated in FIG. 5may be used, for example.

In FIG. 5, (a) is a side view illustrating the preparation device A, and(b) is a top view illustrating the preparation device A.

Reference sign 11 indicates a cap, reference sign 12 indicates anopening that allow gaseous molecules to pass through, reference sign 13indicates a container main body, reference sign 14 indicates a solventsolution of the organic compound (α), and reference sign 15 indicates asingle crystal of a polymer-metal complex.

The cap (11) is not particularly limited as long as the container can beclosed air-tightly. For example, a cap made of rubber (e.g., septum) maybe used as the cap (11). The opening (12) may be formed by inserting adegassing hollow needle into the cap (11), for example. A container madeof glass (e.g., test tube or pressure-resistant glass bottle) may beused as the container main body (13), for example. The bottom of thecontainer main body (13) may be flat. Note that it is preferable thatthe bottom of the container main body (13) have a pointed shape (see (a)in FIG. 5) since the crystal can be easily placed and removed (i.e.,excellent operability is achieved). When a transparent container is usedas the container main body (13), it is possible to easily observe thevolatilization state of the solvent and a change in color of the crystal(i.e., the color of the crystal changes when the guest molecules areintroduced into the pores and the voids of the polymer-metal complex)from the outside.

When using the preparation device A illustrated in FIG. 5 (see (a) and(b)), the solvent included in the solvent solution (14) of the organiccompound (α) gradually volatilizes through the thin opening (12)(degassing hollow needle), and is completely removed from the organiccompound (α). After opening the cap (11) (sealing plug), the crystalstructure analysis sample is removed from the container main body (vial)(13), and crystal structure analysis is performed using the crystalstructure analysis sample.

In FIG. 5, (c) is a side view illustrating the preparation device B, and(d) is a top view illustrating the preparation device B.

As illustrated in FIG. 5 (see (c) and (d)), the preparation device Bincludes an airtight container that includes a cap (11), a containermain body (13), and an opening (12) that allow gaseous molecules to passthrough, and a crystal support (16) that is secured on the cap, and isconfigured so that a single crystal (15) of a polymer-metal complex thatincludes a ligand having two or more coordinating moieties, and a metalion that serves as a center metal, and has a three-dimensional networkstructure can be secured on the front end of the crystal support (16),and the front end of the crystal support (16) is situated downwardinside the container when the container is closed.

The preparation device B illustrated in FIG. 5 (see (c)) is configuredso that the single crystal (15) of the polymer-metal complex is securedon the front end of the crystal support (16) using a cryoloop (notillustrated in FIG. 5).

It is preferable that the preparation device B be configured so that itis possible to introduce the organic compound (α) into the pores and thevoids of the polymer-metal complex to obtain a crystal structureanalysis sample, and transfer the crystal structure analysis sampledirectly to a crystal structure analyzer such as an X-ray crystalstructure analyzer to perform measurement.

4) Method for Determining Molecular Structure of Organic Compound

A method for determining the molecular structure of an organic compoundaccording to one embodiment of the invention includes analyzing thecrystal structure of a crystal structure analysis sample obtained usingthe method for preparing a crystal structure analysis sample accordingto one embodiment of the invention to determine the molecular structureof the organic compound included in the pores and the voids of thecrystal structure analysis sample.

The method for determining the molecular structure of an organiccompound according to one embodiment of the invention may utilize X-raydiffraction or neutron diffraction.

When determining the molecular structure of the organic compound usingthe method for determining the molecular structure of an organiccompound according to one embodiment of the invention, a known methodmay be used, except that the crystal structure analysis sample obtainedusing the method for preparing a crystal structure analysis sampleaccording to one embodiment of the invention is mounted instead of aknown single crystal.

The method for determining the molecular structure of an organiccompound according to one aspect of the invention can efficientlyanalyze the crystal structure of an organic compound, and determine themolecular structure of the organic compound even when the amount of theorganic compound is very small.

The method for determining the molecular structure of an organiccompound according to one aspect of the invention can determine themolecular structure of an organic compound that is liquid at roomtemperature by utilizing the crystal structure analysis sample thatincludes the organic compound.

The organic compound used to prepare the sample may be a gas, a liquid,or a solid. The organic compound can be introduced into the singlecrystal of the polymer-metal complex as long as the organic compound canbe dissolved in an organic solvent.

The amount of the organic compound required for one piece of the singlecrystal of the polymer-metal complex may be 5 μg or less. A singlecrystal structure can be obtained even when the amount of the organiccompound is 50 ng.

It is possible to promptly and accurately determine the structure of atrace amount of impurities, essence, and food additive included in amedicine, a trace component included in animals and plants, and the likeby utilizing the method for determining the molecular structure of anorganic compound according to one embodiment of the invention. It isalso possible to determine the steric structure (absolute structure) ofan unstable compound that easily undergoes thermal decomposition orsolvolysis without heating the compound, or dissolving the compound in asolvent, a buffer, or the like.

EXAMPLES

The invention is further described below by way of examples. Note thatthe invention is not limited to the following examples.

Equipment

(1) X-Ray Single Crystal Structure Analysis

X-ray single crystal structure analysis was performed using an APEXII/CCD diffractometer (manufactured by Bruker, radiation source: Mo-Kαradiation (wavelength: 0.71 Å), output: 50 mA, 24 kV).

(2) Elemental Analysis

Elemental analysis was performed using an analyzer “MT-6” (manufacturedby YANACO).

Example 1: Synthesis of Polymer-Metal Complex Crystal IncludingCyclohexane

Step 1: Synthesis of Polymer-Metal Complex Crystal Including CrystallineSolvent (Nitrobenzene)

50.2 mg (0.16 mmol) of 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) wasdissolved in a nitrobenzene/methanol (32 mL/4 mL) mixture to prepare aligand solution. A metal solution prepared by dissolving 76.5 mg (0.24mmol) of ZnI₂ in 8 mL of methanol was mixed with the ligand solution atroom temperature. The mixture was stirred for 30 seconds, and aprecipitate (white crystals) was filtered off to obtain 151.7 mg of awhite powder (yield: 81.6%).

The resulting white powdery sample was identified by elemental analysisand thermogravimetry-mass spectrometry (TG-MS), and found to be[(ZnI₂)₃(TPT)₂(PhNO₂)_(5.5)]_(n) (polymer-metal complex 1).

Elemental Analysis Results

Cald.: C: 36.68%, H: 2.30%, N: 10.85%.

Found: C: 36.39%, H: 2.43%, N: 10.57%.

Step 2: Synthesis of Polymer-Metal Complex Crystal Including GuestMolecule (Cyclohexane)

The polymer-metal complex 1 (polymer-metal complex crystal includingnitrobenzene) obtained in the step 1 was immersed in cyclohexane in aratio of 100 mg/10 mL. The mixture was heated to 45° C. using anincubator, and allowed to stand for 1 week. The supernatant liquid(cyclohexane) was exchanged by decantation every other day during thisperiod.

When 1 week had elapsed, the single crystal was removed, and identifiedby elemental analysis and crystal structure analysis. It was found thatthe single crystal was [(ZnI₂)₃(TPT)₂(cyclohexane)₄].

The elemental analysis results are shown below. Table 1 shows thecrystallographic data.

FIG. 6 shows a micrograph of the single crystal.

Note that the occupancy ratio of cyclohexane was 100%.

TABLE 1 Crystal system Monoclinic Space group C2/c a (Å) 34.559 b (Å)15.111 c (Å) 30.058 α (°) 90 β (°) 100.510 γ (°) 90 Z 8 R1 11.48Elemental Analysis Results

Found: C: 37.67%, H: 3.53%, N: 8.75%.

Cald.: C: 37.56%, H: 3.78%, N: 8.76%.

FIGS. 7 and 8 show the crystal structure of the resulting polymer-metalcomplex crystal including cyclohexane.

Example 2: Synthesis of Polymer-Metal Complex Crystal Including EthylAcetate

10 mg of the single crystal of the polymer-metal complex 1 obtained inthe step 1 of Example 1 was immersed in 10 mL of ethyl acetate for 7days under the same conditions as those employed in the step 2 ofExample 1 to saturate the pores and the like of the single crystal withethyl acetate. The resulting complex crystal was filtered off, andsubjected to elemental analysis. It was thus found that the complexcrystal was a polymer-metal complex [(ZnI₂)₃(TPT)₂(AcOEt)₃] in whichethyl acetate (AcOEt) was included in the pores and the like.

Elemental Analysis Results

Found: C: 31.36%, H: 2.38%, N: 9.30%.

Cald.: C: 31.22%, H: 2.62%, N: 9.10%.

Example 3: Synthesis of Polymer-Metal Complex Crystal Including Heptane

10 mg of the single crystal of the polymer-metal complex 1 obtained inthe step 1 of Example 1 was immersed in 10 mL of heptane for 7 daysunder the same conditions as those employed in the step 2 of Example 1to saturate the pores and the like of the single crystal with heptane.The resulting complex crystal was filtered off, and subjected toelemental analysis. It was thus found that the complex crystal was apolymer-metal complex [(ZnI₂)₃(TPT)₂(PhNO₂)(heptane)_(2.5)] in whichheptane was included in the pores and the like.

Elemental Analysis Results

Found: C: 36.68%, H: 3.60%, N: 9.43%.

Cald.: C: 36.54%, H: 3.56%, N: 9.31%.

Example 4: Synthesis of Polymer-Metal Complex Crystal Including Toluene

10 mg of the single crystal of the polymer-metal complex 1 obtained inthe step 1 of Example 1 was immersed in 10 mL of toluene for 7 daysunder the same conditions as those employed in the step 2 of Example 1to saturate the pores and the like of the single crystal with toluene.The resulting complex crystal was filtered off, and subjected toelemental analysis. It was thus found that the complex crystal was apolymer-metal complex [(ZnI₂)₃(TPT)₂(toluene)₅] in which toluene wasincluded in the pores and the like.

Elemental Analysis Results

Found: C: 42.12%, H: 3.04%, N: 8.26%.

Cald.: C: 41.74%, H: 3.16%, N: 8.23%.

Example 5: Synthesis of Polymer-Metal Complex Crystal Including1,2-Dimethoxyethane

10 mg of the single crystal of the polymer-metal complex 1 obtained inthe step 1 of Example 1 was immersed in 10 mL of 1,2-dimethoxyethane(DME) for 7 days under the same conditions as those employed in the step2 of Example 1 to saturate the pores and the like of the single crystalwith DME. The resulting complex crystal was filtered off, and subjectedto elemental analysis. It was thus found that the complex crystal was apolymer-metal complex [(ZnI₂)₃(TPT)₂(DME)_(2.5)] in which DME wasincluded in the pores and the like.

Elemental Analysis Results

Found: C: 30.87%, H: 2.53%, N: 9.07%.

Cald.: C: 30.57%, H: 2.73%, N: 9.30%.

Example 6: Synthesis of Polymer-Metal Complex Crystal IncludingAcetonitrile

10 mg of the single crystal of the polymer-metal complex 1 obtained inthe step 1 of Example 1 was immersed in 10 mL of acetonitrile (CH₃CN)for 7 days under the same conditions as those employed in the step 2 ofExample 1 to saturate the pores and the like of the single crystal withCH₃CN. The resulting complex crystal was filtered off, and subjected toelemental analysis. It was thus found that the complex crystal was apolymer-metal complex [(ZnI₂)₃(TPT)₂(CH₃CN)_(3.25)] in which CH₃CN wasincluded in the pores and the like.

Elemental Analysis Results

Found: C: 29.92%, H: 1.68%, N: 12.19%.

Cald.: C: 29.75%, H: 1.98%, N: 12.45%.

Example 7: Synthesis of Polymer-Metal Complex Crystal Including CarbonTetrachloride

10 mg of the single crystal of the polymer-metal complex 1 obtained inthe step 1 of Example 1 was immersed in 10 mL of carbon tetrachloride(CCl₄) for 7 days under the same conditions as those employed in thestep 2 of Example 1 to saturate the pores and the like of the singlecrystal with carbon tetrachloride. The resulting complex crystal wasfiltered off, and subjected to elemental analysis. It was thus foundthat the complex crystal was a polymer-metal complex[(ZnI₂)₃(TPT)₂(CCl₄)₅] in which carbon tetrachloride was included in thepores and the like.

Elemental Analysis Results

Found: C: 20.77%, H: 0.75%, N: 6.93%.

Cald.: C: 20.94%, H: 1.03%, N: 7.15%.

Example 8: Synthesis of Polymer-Metal Complex Including Cyclohexane

6.3 mg of TPT was dissolved in a nitrobenzene/methanol (4 mL/1 mL)mixture to obtain a ligand solution.

Separately, 9.6 mg of ZnI₂ was dissolved in 1 mL of methanol to obtain ametal ion-containing solution.

The ligand solution was put in a test tube (diameter: 15 mm, height: 12cm), and the metal ion-containing solution was slowly added to the testtube so as to form a layer on the ligand solution. The solutions wereallowed to stand at 15 to 25° C. for 7 days to obtain a polymer-metalcomplex crystal.

The resulting crystal was identified by elemental analysis,thermogravimetry-mass spectrometry, and X-ray single crystal structureanalysis in the same manner as in Example 1, and found to be[(ZnI₂)₃(TPT)₂(PhNO₂)_(5.5)]_(n).

100 mg of the single crystal of the polymer-metal complex includingnitrobenzene obtained as described above was immersed in 10 mL ofcyclohexane for 2 days under the same conditions as those employed inExample 1 to saturate the pores of the single crystal with cyclohexane.The single crystal was then removed, and subjected to elemental analysisand crystal structure analysis. It was found that the single crystal wasa compound having the composition [(ZnI₂)₃(TPT)₂(cyclohexane)₄]_(n).

Example 9: Synthesis of Polymer-Metal Complex Crystal IncludingDichlorobenzene

6.3 mg of TPT was dissolved in 5 mL of a 1,2-dichlorobenzene/methanol(volume ratio: 4:1) mixture in a test tube. A solution prepared bydissolving 7.0 mg of cobalt(II) thiocyanate in 1 mL of methanol wasslowly added to the above solution, and the solutions separated in twolayers were allowed to stand at room temperature for 2 days.

An orange crystal that precipitated on the wall of the test tube wasfiltered off to obtain 9.9 mg of a polymer-metal complex (yield: 52%).

The resulting polymer-metal complex was subjected to elemental analysisand X-ray single crystal structural analysis, and found to be(TPT)₄{Co(SCN)₂}₃(Cl₂C₆H₄)_(2.5)(MeOH)₅ having the same structure asthat illustrated in FIG. 4. The polymer-metal complex includedtwenty-five 1,2-dichlorobenzene molecules and five methanol moleculesper regular octahedral structural unit.

Elemental Analysis Results

Found: C: 49.60%, H: 2.92%, N: 7.43%.

Cald.: C: 49.89%, H: 3.02%, N: 7.48%.

X-Ray Single Crystal Structural Analysis Results

Lattice constant: a=b=c=37.599 Å, cubic, space group: Fm-3m

Example 10: Synthesis of Polymer-Metal Complex Crystal Including2-methyl-1,4-naphthoquinone

A micro vial with a septum cap was charged with 50 μL of ethyl acetate,and one piece (size: 150×150×100 μm, theoretical amount of a substancehaving a specific gravity of 1 required to fill the pores therewith:1.13 μg) of the single crystal of the polymer-metal complex includingethyl acetate ([(ZnI₂)₃(TPT)₂(AcOEt)₃]) obtained in Example 2 wasimmersed in ethyl acetate contained in the micro vial.

2-Methyl-1,4-naphthoquinone was dissolved in dichloromethane at aconcentration of 1 μg/1 μL, and 5 μL of the resulting sample solution(including 2-methyl-1,4-naphthoquinone in an amount of 5 μg) was addedto the micro vial. The value A in Example 10 was 4.4.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (ethyl acetate and dichloromethane) contained in themicro vial volatilized at a volatilization rate of about 48 μL/24 hoursunder the above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

Tables 2 shows the crystallographic data, and FIGS. 9 and 10 show thecrystal structure.

TABLE 2 Crystal system Triclinic Space group P-1 a (Å) 14.991 b (Å)18.774 c (Å) 30.118 α (°) 98.981 β (°) 92.187 γ (°) 110.596 Z 2 R1 13.31

Example 11: Synthesis of Polymer-Metal Complex Crystal Including4-cyano-4′-pentylbiphenyl

A micro vial with a septum cap was charged with 50 μL of heptane, andone piece (size: 200×60×50 μm, theoretical amount of a substance havinga specific gravity of 1 required to fill the pores therewith: 0.30 μg)of the single crystal of the polymer-metal complex including heptane([(ZnI₂)₃(TPT)₂(nitrobenzene)(heptane)_(2.5)]) obtained in Example 2 wasimmersed in heptane contained in the micro vial.

4-Cyano-4′-pentylbiphenyl was dissolved in dichloromethane at aconcentration of 1 μg/1 μL, and 5 μL of the resulting sample solution(including 4-cyano-4′-pentylbiphenyl in an amount of 5 μg) was added tothe micro vial. The value A in Example 11 was 16.6.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (heptane and dichloromethane) contained in the microvial volatilized at a volatilization rate of about 48 μL/24 hours underthe above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

Tables 3 shows the crystallographic data, and FIGS. 11 and 12 show thecrystal structure.

TABLE 3 Crystal system Monoclinic Space group C2/c a (Å) 35.562 b (Å)14.7759 c (Å) 31.573 α (°) 90 β (°) 102.981 γ (°) 90 Z 8 R1 7.54

Example 12: Synthesis of Polymer-Metal Complex Crystal Including1,4-dimethyl-7-isopropylazulene

A micro vial with a septum cap (see (a) in FIG. 5) was charged with 50μL of cyclohexane, and one piece (size: 100×100×60 μm, theoreticalamount of a substance having a specific gravity of 1 required to fillthe pores therewith: 0.3 μg) of the single crystal of the polymer-metalcomplex including cyclohexane obtained in Example 8 was immersed incyclohexane contained in the micro vial.

1,4-Dimethyl-7-isopropylazulene was dissolved in dichloromethane at aconcentration of 1 μg/1 μL, and 5 μL of the resulting sample solution(including 1,4-dimethyl-7-isopropylazulene in an amount of 5 μg) wasadded to the micro vial. The value A in Example 12 was 16.7.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (cyclohexane and dichloromethane) contained in themicro vial volatilized at a volatilization rate of about 48 μL/24 hoursunder the above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

The diffraction pattern illustrated in FIG. 13 was obtained at anexposure time of 30 seconds, and the resolution was 0.8 Å or more.

Tables 4 shows the crystallographic data, and FIGS. 14 and 15 show thecrystal structure. Note that the occupancy ratio of1,4-dimethyl-7-isopropylazulene was 73%.

TABLE 4 Crystal system Monoclinic Space group C2/c a (Å) 34.942 b (Å)14.8462 c (Å) 30.976 α (°) 90 β (°) 102.149 γ (°) 90 Z 8 R1 10.6

Example 13: Synthesis of Polymer-Metal Complex Crystal Including(3S,3aS,5aS,9bS)-3a,5,5a,9b-tetrahydro-3,5a,9-trimethylnaphtho[1,2-b]furan-2,8(3H,4H)-dione

A micro vial with a septum cap (see (a) in FIG. 5) was charged with 50μL of cyclohexane, and one piece (size: 350×70×50 μm, theoretical amountof a substance having a specific gravity of 1 required to fill the porestherewith: 0.61 μg) of the single crystal obtained in Example 8 wasimmersed in cyclohexane contained in the micro vial.

(3S,3aS,5aS,9bS)-3a,5,5a,9b-Tetrahydro-3,5a,9-trimethylnaphtho[1,2-b]furan-2,8(3H,4H)-dionewas dissolved in dichloromethane at a concentration of 1 μg/1 μL, and 5μL of the resulting sample solution (including(3S,3aS,5aS,9bS)-3a,5,5a,9b-tetrahydro-3,5a,9-trimethylnaphtho[1,2-b]furan-2,8(3H,4H)-dionein an amount of 5 μg) was added to the micro vial. The value A inExample 13 was 8.2.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (cyclohexane and dichloromethane) contained in themicro vial volatilized at a volatilization rate of about 48 μL/24 hoursunder the above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

Tables 5 shows the crystallographic data, and FIGS. 16 and 17 show thecrystal structure. Note that the occupancy ratio of(3S,3aS,5aS,9bS)-3a,5,5a,9b-tetrahydro-3,5a,9-trimethylnaphtho[1,2-b]furan-2,8(3H,4H)-dionewas 100%.

TABLE 5 Crystal system Monoclinic Space group P2₁ a (Å) 32.866 b (Å)14.853 c (Å) 34.85 α (°) 90 β (°) 105.848 γ (°) 90 Z 2 R1 8.27

Example 14: Synthesis of Polymer-Metal Complex Crystal Including2-(3,4-dimethoxyphenyl)-5,6,7,8-tetramethoxy-4H-1-benzopyran-4-one

A micro vial with a septum cap (see (a) in FIG. 5) was charged with 50μL of cyclohexane, and one piece (size: 130×110×80 μm, theoreticalamount of a substance having a specific gravity of 1 required to fillthe pores therewith: 0.57 μg) of the single crystal obtained in Example8 was immersed in cyclohexane contained in the micro vial.

2-(3,4-Dimethoxyphenyl)-5,6,7,8-tetramethoxy-4H-1-benzopyran-4-one wasdissolved in dichloromethane at a concentration of 1 μg/1 μL, and 5 μLof the resulting sample solution (including2-(3,4-dimethoxyphenyl)-5,6,7,8-tetramethoxy-4H-1-benzopyran-4-one in anamount of 5 μg) was added to the micro vial. The value A in Example 14was 8.8.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (cyclohexane and dichloromethane) contained in themicro vial volatilized at a volatilization rate of about 48 μL/24 hoursunder the above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

Tables 6 shows the crystallographic data, and FIGS. 18 and 19 show thecrystal structure. Note that the occupancy ratio of2-(3,4-dimethoxyphenyl)-5,6,7,8-tetramethoxy-4H-1-benzopyran-4-one was53%.

TABLE 6 Crystal system Monoclinic Space group C2/c a (Å) 34.562 b (Å)14.95 c (Å) 30.348 α (°) 90 β (°) 100.119 γ (°) 90 Z 8 R1 13.13

Example 15: Synthesis of Polymer-Metal Complex Crystal Including5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one

A micro vial with a septum cap (see (a) in FIG. 5) was charged with 50μL of cyclohexane, and one piece (size: 300×100×100 μm, theoreticalamount of a substance having a specific gravity of 1 required to fillthe pores therewith: 1.5 μg) of the single crystal obtained in Example 8was immersed in cyclohexane contained in the micro vial.

5,6,7,8-Tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one wasdissolved in dichloromethane at a concentration of 2 μg/1 μL, and 2.5 μLof the resulting sample solution (including5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one in anamount of 5 μg) was added to the micro vial. The value A in Example 15was 3.3.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (cyclohexane and dichloromethane) contained in themicro vial volatilized at a volatilization rate of about 48 μL/24 hoursunder the above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

Tables 7 shows the crystallographic data, and FIGS. 20 and 21 show thecrystal structure. Note that the occupancy ratio of5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one was 80%.

TABLE 7 Crystal system Monoclinic Space group C2/c a (Å) 34.103 b (Å)14.767 c (Å) 30.7 α (°) 90 β (°) 99.802 γ (°) 90 Z 8 R1 9.52

Example 16

100 mg of the single crystal of the cobalt complex obtained in Example 9was immersed in 10 mL of toluene for 2 days to saturate the pores of thesingle crystal with toluene.

A micro vial with a septum cap (see (a) in FIG. 5) was charged with 50μL of toluene, and one piece (size: 320×300×280 μm, theoretical amountof a substance having a specific gravity of 1 required to fill the porestherewith: 21.0 μg) of the single crystal that had been immersed intoluene, was immersed in toluene contained in the micro vial. The valueA in Example 16 was 0.31.

2,2′-Bithiophene was dissolved in toluene at a concentration of 1 μg/1μL, and 5 μL of the resulting sample solution (including2,2′-bithiophene in an amount of 5 μg was added to the micro vial.

After allowing the mixture to stand at 45° C. for 2 days, the singlecrystal was removed, mounted on an X-ray crystal structure analyzer, andsubjected to crystal structure analysis.

Tables 8 shows the crystallographic data, and FIGS. 22 and 23 show thecrystal structure. Note that the occupancy ratio of 2,2′-bithiophene was100%.

TABLE 8 Crystal system Tetragonal Space group P42/mnm a (Å) 26.58 b (Å)26.58 c (Å) 36.273 α (°) 90 β (°) 90 γ (°) 90 Z 16 R1 11.08

Comparative Example 1

10 mg of the single crystal of the polymer-metal complex 1 obtained inthe step 1 of Example 1 was immersed in 10 mL of cyclohexane for 2 daysunder the same conditions as those employed in the step 2 of Example 1to obtain a single crystal 1r of a polymer-metal complex.

The resulting polymer complex was dissolved in hydrochloric acid,extracted with deuterated chloroform, and subjected to NMR measurement.As a result, only nitrobenzene and cyclohexane were observed in a ratio(cyclohexane:nitrobenzene) of 39:61.

A micro vial with a septum cap was charged with 50 μL of cyclohexane,and one piece (size: 150×130×120 μm, theoretical amount of a substancehaving a specific gravity of 1 required to fill the pores therewith:1.17 μg) of the resulting single crystal was immersed in cyclohexanecontained in the micro vial.

5,6,7,8-Tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one wasdissolved in dichloromethane at a concentration of 1 μg/1 μL, and 5 μLof the resulting sample solution (including5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one in anamount of 5 μg) was added to the micro vial. The value A in ComparativeExample 1 was 3.3.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (cyclohexane and dichloromethane) contained in themicro vial volatilized at a volatilization rate of about 48 μL/24 hoursunder the above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

Tables 9 shows the crystallographic data, and FIGS. 24 and 25 show thecrystal structure.

It was found that nitrobenzene remained included in the crystal, and5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one was notincluded in the crystal.

TABLE 9 Crystal system Monoclinic Space group C2/c a (Å) 34.534 b (Å)15.033 c (Å) 30.376 α (°) 90 β (°) 101.559 γ (°) 90 Z 8 R1 7.72

Comparative Example 2

An experiment was performed in the same manner as in Comparative Example1, except that one piece (size: 150×130×120 μm, theoretical amount of asubstance having a specific gravity of 1 required to fill the porestherewith: 1.17 μg) of the single crystal of the polymer-metal complex 1obtained in the step 1 of Example 1 was used.

A micro vial with a septum cap was charged with 50 μL of cyclohexane,and one piece of the single crystal was immersed in cyclohexanecontained in the micro vial.

5,6,7,8-Tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one wasdissolved in dichloromethane at a concentration of 1 μg/1 μL, and 5 μLof the resulting sample solution (including5,6,7,8-tetramethoxy-2-(4-methoxyphenyl)-4H-1-benzopyran-4-one in anamount of 5 μg) was added to the micro vial. The value A in ComparativeExample 2 was 3.3.

After fastening the cap on the micro vial, a pinhole was formed in theseptum using a syringe needle (hole diameter: 0.8 mm), and the microvial was allowed to stand in a temperature-controlled room at 45° C. for2 days.

The organic solvent (cyclohexane and dichloromethane) contained in themicro vial volatilized at a volatilization rate of about 48 μL/24 hoursunder the above conditions, and the solution was concentrated.

The single crystal was then removed, mounted on an X-ray crystalstructure analyzer, and subjected to crystal structure analysis.

A crystal structure in which nitrobenzene was included in the pores wasobtained in the same manner as in Comparative Example 1.

Example 17

100 mg of the single crystal of the polymer-metal complex obtained inthe step 1 of Example 1 was immersed in 10 mL of cyclohexane at 25° C.for 7 days to saturate the pores of the single crystal withcyclohexanone to obtain a polymer-metal complex crystal includingcyclohexane.

As illustrated in FIG. 26, the polymer-metal complex crystal was placedon a glass plate, and one drop (about 100 μg) of isoprene (orcyclohexane) was dropped onto the complex using a dropper. Thepolymer-metal complex crystal was transferred to a micro vial with aseptum cap (not illustrated in FIG. 26), and the micro vial was placedin a temperature-controlled room at 25° C. for 2 days to obtain acrystal structure analysis sample.

The resulting sample was removed, mounted on an X-ray crystal structureanalyzer, and subjected to crystal structure analysis.

FIG. 27 is an enlarged view showing the crystal structure of thepolymer-metal complex including isoprene.

Example 18

100 mg of the single crystal of the cobalt complex obtained in Example 9was immersed in 10 mL of toluene at 25° C. for 7 days to saturate thepores of the single crystal with toluene to obtain a polymer-metalcomplex crystal including toluene.

As illustrated in FIG. 26, the polymer-metal complex crystal was placedon a glass plate, and one drop (about 100 μg) of cyclohexanone wasdropped onto the complex using a dropper. The polymer-metal complexcrystal was allowed to stand in a temperature-controlled room at 25° C.for 2 days to obtain a crystal structure analysis sample.

The resulting sample was removed, mounted on an X-ray crystal structureanalyzer, and subjected to crystal structure analysis.

FIG. 28 is an enlarged view showing the crystal structure of thepolymer-metal complex including cyclohexanone.

It was confirmed from the results of Examples 17 and 18 that the crystalstructure of a liquid organic compound could be analyzed in the samemanner as that of a crystal.

REFERENCE SIGNS LIST

-   1: Crystal plane X-   2: Crystal plane Y-   3: Pore-   4: Extension direction of pore-   11: Cap (septum cap)-   11 a: Septum-   11 b: Plastic part-   12: Opening (degassing hollow needle)-   13: Container main body (vial)-   14: Solvent solution of organic compound (α)-   15: Single crystal of polymer-metal complex-   16: Crystal support

The invention claimed is:
 1. A method for preparing a crystal structureanalysis sample in which a molecule of an organic compound for which amolecular structure is to be determined, is arranged in pores and voidsof a polymer-metal complex crystal in an ordered manner, the methodcomprising: immersing a polymer-metal complex crystal including a guestcompound in a solvent solution that includes the organic compound, thepolymer-metal complex crystal including a guest compound being thepolymer-metal complex crystal comprising a polymer-metal complex thatcomprises a ligand having two or more coordinating moieties, and a metalion that serves as a center metal, the polymer-metal complex having athree-dimensional network structure that is formed by the metal ion andthe ligand that is coordinated to the metal ion, and having pores andvoids that are three-dimensionally arranged in the three-dimensionalnetwork structure in an ordered manner, at least one compound selectedfrom a group consisting of an aliphatic hydrocarbon, an alicyclichydrocarbon, an ether, an ester, an aromatic hydrocarbon, a halogenatedhydrocarbon, and a nitrile being included in the pores and the voids asa guest compound (A), and a ratio of an amount of the guest compound (A)present in the pores and the voids to a total amount of the guestcompound included in the pores and the voids being 60 mol % or more. 2.The method for preparing a crystal structure analysis sample accordingto claim 1, the method comprising immersing the polymer-metal complexcrystal including the guest compound (A) in the solvent solution thatincludes the organic compound in an amount of 100 μg or less so that avalue A calculated by an expression (2) is 0.1 to 30, $\begin{matrix}{A = \frac{b}{a}} & (2)\end{matrix}$ where, b is an amount of the organic compound included inthe solvent solution, and a is an amount of a substance having aspecific gravity of 1 that is required to fill all of the pores and thevoids of the polymer-metal complex crystal with the substance having aspecific gravity of
 1. 3. The method for preparing a crystal structureanalysis sample according to claim 1, wherein a concentration of theorganic compound in the solvent solution is 0.001 to 50 μg/μL.
 4. Themethod for preparing a crystal structure analysis sample according toclaim 1, wherein the organic compound is impurities included in acompound derived from a natural product, or a synthetic compound.
 5. Themethod for preparing a crystal structure analysis sample according toclaim 1, the method comprising volatilizing the solvent after immersingthe polymer-metal complex crystal including a guest compound in thesolvent solution that includes the organic compound to concentrate thesolvent solution.
 6. The method for preparing a crystal structureanalysis sample according to claim 5, wherein a volatilization rate ofthe solvent is 0.1 to 1000 μL/24 hours.
 7. The method for preparing acrystal structure analysis sample according to claim 5, wherein thesolvent is volatilized at 0 to 180° C.
 8. The method for preparing acrystal structure analysis sample according to claim 1, wherein theimmersing of the polymer-metal complex crystal including a guestcompound in the solvent solution that includes the organic compoundincludes immersing one piece of the polymer-metal complex crystalincluding a guest compound in the solvent solution that includes theorganic compound.
 9. The method for preparing a crystal structureanalysis sample according to claim 1, the method comprising: a step (I)that separates a mixture that includes an organic compound for which amolecular structure is to be determined, by liquid chromatography toobtain a solvent solution of the organic compound for which themolecular structure is to be determined; and a step (II) that immersesthe polymer-metal complex crystal including a guest compound in thesolvent solution of the organic compound for which the molecularstructure is to be determined, that has been obtained in the step (I),and volatilizes the solvent under moderate conditions to concentrate thesolvent solution.
 10. The method for preparing a crystal structureanalysis sample according to claim 1, wherein a molecular structure ofthe resulting crystal structure analysis sample can be determined with aresolution of at least 1.5 Å by applying MoKα radiation (wavelength:0.71 Å) generated at a tube voltage of 24 kV and a tube current of 50 mAto the crystal structure analysis sample, and detecting diffractedX-rays using a CCD detector.
 11. The method for preparing a crystalstructure analysis sample according to claim 1, wherein the guestcompound (A) is an alicyclic hydrocarbon having 3 to 20 carbon atoms oran aromatic hydrocarbon having 6 to 10 carbon atoms.
 12. The method forpreparing a crystal structure analysis sample according to claim 1,wherein the guest compound (A) is a saturated alicyclic hydrocarbonhaving 3 to 20 carbon atoms.
 13. The method for preparing a crystalstructure analysis sample according to claim 1, wherein a totaloccupancy ratio of the guest compound included in the pores and thevoids of the polymer-metal complex is 10% or more.
 14. The method forpreparing a crystal structure analysis sample according to claim 1,wherein the ligand having two or more coordinating moieties is anorganic ligand having three or more coordinating moieties, and the metalion that serves as the center metal is a cobalt ion or a zinc ion. 15.The method for preparing a crystal structure analysis sample accordingto claim 1, wherein the polymer-metal complex is a compound representedby [[M(X)₂]₃(L)₂]_(n) (wherein M is a metal ion, X is a monovalentanion, L is a tridentate ligand represented by a formula (1),

wherein Ar is a substituted or unsubstituted trivalent aromatic group,X¹ to X³ are independently a divalent organic group, or a single bondthat directly bonds Ar and Y¹, Y², or Y³, and Y¹ to Y³ are independentlya monovalent organic group having a coordinating moiety, and n is anarbitrary natural number).
 16. The method for preparing a crystalstructure analysis sample according to claim 1, wherein the metal ion isan ion of a metal among the metals that belong to Groups 8 to 12 in theperiodic table.
 17. The method for preparing a crystal structureanalysis sample according to claim 1, wherein the metal ion is azinc(II) ion or a cobalt(II) ion.
 18. The method for preparing a crystalstructure analysis sample according to claim 1, wherein thepolymer-metal complex crystal has a cubic or cuboidal shape with a sidelength of 10 to 1000 μm.
 19. The method for preparing a crystalstructure analysis sample according to claim 1, the method comprisingimmersing a polymer-metal complex crystal including a crystallizationsolvent in the guest compound (A) in a liquid state, or an inert solventsolution that includes the guest compound (A), the polymer-metal complexcrystal including a crystallization solvent comprising a polymer-metalcomplex that comprises a ligand having two or more coordinatingmoieties, and a metal ion that serves as a center metal, thepolymer-metal complex having a three-dimensional network structure thatis formed by the metal ion and the ligand that is coordinated to themetal ion, and having pores and voids that are three-dimensionallyarranged in the three-dimensional network structure in an orderedmanner, a crystallization solvent (excluding the guest compound (A))being included in the pores and the voids.
 20. A method for determininga molecular structure of an organic compound comprising analyzing acrystal structure of a crystal structure analysis sample obtained usingthe method for preparing a crystal structure analysis sample accordingto claim 1 to determine a molecular structure of an organic compoundincluded in the pores and the voids of the crystal structure analysissample.